TW201630847A - Fiber sizing agent composition, fiber sizing agent dispersion, fiber sizing agent solution, method for producing fiber bundles, composite intermediate and fiber-reinforced composite material - Google Patents

Fiber sizing agent composition, fiber sizing agent dispersion, fiber sizing agent solution, method for producing fiber bundles, composite intermediate and fiber-reinforced composite material Download PDF

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TW201630847A
TW201630847A TW104129098A TW104129098A TW201630847A TW 201630847 A TW201630847 A TW 201630847A TW 104129098 A TW104129098 A TW 104129098A TW 104129098 A TW104129098 A TW 104129098A TW 201630847 A TW201630847 A TW 201630847A
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fiber
sizing agent
acid
polyester resin
fiber sizing
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TWI702194B (en
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Sayaka Sakaguchi
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Sanyo Chemical Ind Ltd
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    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
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    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
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    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
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    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
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    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
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    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
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    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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Abstract

The present invention is a fiber sizing agent composition comprising a polyester resin (A) and a reactive compound (B), wherein the polyester resin (A) has an HLB of 4 to 18 and a viscosity at 30 DEG C of 10 to 1,000,000 Pas, the reactive compound (B) is at least one reactive compound selected from the group consisting of block isocyanates, tertiary amines, tertiary amine salts, quaternary ammonium salts, quaternary phosphonium salts, and phosphine compounds, and the weight ratio [(A)/(B)]of the polyester resin (A) and the reactive compound (B) in the fiber sizing agent composition is 99.9/0.1 to 10/90.

Description

纖維用集束劑組成物、纖維用集束劑分散體、纖維用集束劑溶液、纖維束之製造方法、複合中間體及纖維強化複合材料 Fiber sizing agent composition, fiber sizing agent dispersion, fiber sizing agent solution, fiber bundle manufacturing method, composite intermediate, and fiber reinforced composite material

本發明係關於一種纖維用集束劑組成物。更詳細而言，本發明係關於一種纖維強化複合材料中所使用之纖維用集束劑組成物。 The present invention relates to a sizing agent composition for fibers. More specifically, the present invention relates to a fiber sizing agent composition used in a fiber-reinforced composite material.

不飽和聚酯樹脂、酚樹脂及環氧樹脂等基質樹脂與各種纖維之複合材料，被廣泛用於建築材料、運動用具、娛樂用品及飛機等領域。作為該等複合材料所使用之纖維，可列舉：聚芳醯胺纖維、玻璃纖維、碳纖維、陶瓷纖維、金屬纖維、礦物纖維、岩石纖維及礦渣纖維(slag fiber)等。該等纖維之中，尤其是碳纖維由於拉伸強度優異，故而用於高性能纖維強化複合材料用途。碳纖維通常係以長絲(filament)或絲束之形態製造，進而被加工成沿一方向拉齊之片材、長絲繞組、織物或短切纖維等而使用。於碳纖維之加工中為了防止起毛或斷頭，通常會對長絲或絲束賦予集束劑。 Composite materials such as unsaturated polyester resin, phenol resin and epoxy resin and various fiber materials are widely used in construction materials, sports equipment, entertainment products and aircraft. Examples of the fibers used in the composite materials include polyarmine fibers, glass fibers, carbon fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers, and slag fibers. Among these fibers, carbon fibers are particularly useful for high-performance fiber-reinforced composite materials because of their excellent tensile strength. Carbon fibers are usually produced in the form of filaments or tows, and are processed into sheets that are aligned in one direction, filament windings, woven fabrics or chopped fibers, and the like. In order to prevent fuzzing or breakage during processing of carbon fibers, a sizing agent is usually applied to the filaments or tows.

近年來，為了將複合材料拓展至各種用途，而要求進一步提高其強度。為此，業界正進行對集束劑賦予新的功能而提高複合材料之強度之開發。 In recent years, in order to expand composite materials to various uses, it is required to further increase the strength. To this end, the industry is developing a new function for the sizing agent to increase the strength of the composite material.

例如可列舉：由利用含有特定環氧化合物之集束劑進行過上漿處理 (sizing treatment)之纖維束所構成之複合材料(專利文獻1)、由利用含有具環氧基之橡膠乳膠之集束劑進行過上漿處理之纖維束所構成之複合材料(專利文獻2)、由利用含有封端異氰酸酯之集束劑進行過上漿處理之纖維束所構成之複合材料(專利文獻3及4)。 For example, it can be exemplified by sizing treatment using a sizing agent containing a specific epoxy compound. A composite material composed of a fiber bundle of a sizing treatment (Patent Document 1), a composite material comprising a fiber bundle subjected to sizing treatment using a sizing agent containing a rubber latex having an epoxy group (Patent Document 2), A composite material composed of a fiber bundle subjected to sizing treatment using a sizing agent containing a blocked isocyanate (Patent Documents 3 and 4).

專利文獻1：日本特開2013-177704號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2013-177704

專利文獻2：日本特開2008-95222號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2008-95222

專利文獻3：日本特開平2-84558號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. 2-84558

專利文獻4：日本特開2014-162999號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. 2014-162999

專利文獻1及2中所提出之集束劑存在纖維束之集束性不足，且複合材料之強度亦不足之課題。關於專利文獻3及4中所提出之集束劑，由於纖維束之起毛較多，故而複合材料之強度尚不充分。 The sizing agents proposed in Patent Documents 1 and 2 have a problem that the bundle property of the fiber bundle is insufficient and the strength of the composite material is insufficient. Regarding the sizing agents proposed in Patent Documents 3 and 4, since the fiber bundle has a large amount of fuzz, the strength of the composite material is not sufficient.

本發明之目的在於提供一種可對纖維束賦予優異之集束性，且對使用該纖維束之纖維強化複合材料賦予優異之拉伸強度之纖維用集束劑組成物。 An object of the present invention is to provide a fiber sizing agent composition which imparts excellent bundleability to a fiber bundle and imparts excellent tensile strength to a fiber-reinforced composite material using the fiber bundle.

本發明人為了解決上述課題而反覆進行努力研究，結果完成本發明。即，本發明為一種纖維用集束劑組成物，其含有聚酯樹脂(A)及反應性化合物(B)，並且聚酯樹脂(A)係HLB為4~18、於30℃之黏度為10~1,000,000Pa‧s之聚酯樹脂，反應性化合物(B)為選自由封端異氰酸酯、三級胺、三級胺鹽、四級銨鹽、四級鏻鹽及膦化合物所組成之群中 之至少1種反應性化合物，纖維用集束劑組成物中之聚酯樹脂(A)與反應性化合物(B)之重量比[(A)/(B)]為99.9/0.1~10/90；為一種纖維用集束劑分散體，係使該纖維用集束劑組成物分散於水或有機溶劑中而成；為一種纖維用集束劑溶液，係使該纖維用集束劑組成物溶解於水或有機溶劑中而成；為一種纖維束之製造方法，係利用該纖維用集束劑分散體或該纖維用集束劑溶液對纖維進行處理而獲得纖維束；為一種複合中間體，係由經該製造方法獲得之纖維束與基質樹脂而獲得；及一種纖維強化複合材料，係將該複合中間體成形而成。 The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have completed the present invention. That is, the present invention is a fiber sizing agent composition comprising a polyester resin (A) and a reactive compound (B), and the polyester resin (A) has an HLB of 4 to 18 and a viscosity at 30 ° C of 10 ~1,000,000 Pa ‧ polyester resin, the reactive compound (B) is selected from the group consisting of blocked isocyanate, tertiary amine, tertiary amine salt, quaternary ammonium salt, quaternary phosphonium salt and phosphine compound At least one reactive compound, the weight ratio of the polyester resin (A) to the reactive compound (B) in the fiber sizing agent composition [(A) / (B)] is 99.9 / 0.1 ~ 10 / 90; a fiber sizing agent dispersion obtained by dispersing the fiber in a water or an organic solvent; a fiber sizing agent solution for dissolving the fiber in a water or organic sizing agent composition a method for producing a fiber bundle, wherein the fiber bundle is treated with the fiber sizing agent dispersion or the fiber sizing agent solution to obtain a fiber bundle; and the composite intermediate is a composite method. The obtained fiber bundle and the matrix resin are obtained; and a fiber reinforced composite material is formed by molding the composite intermediate.

本發明之纖維用集束劑組成物之乳化穩定性優異、發揮出對纖維束賦予良好之集束性之效果及抑制起毛產生之效果，使用該纖維束之纖維強化複合材料發揮出拉伸強度優異之效果。 The fiber sizing agent composition of the present invention is excellent in emulsion stability, exhibits an effect of imparting good bundling property to the fiber bundle, and has an effect of suppressing fuzzing, and the fiber-reinforced composite material using the fiber bundle exhibits excellent tensile strength. effect.

本發明之纖維用集束劑組成物係含有聚酯樹脂(A)而成。聚酯樹脂(A)係分子中具有2個以上酯鍵者。 The sizing agent composition for fibers of the present invention contains a polyester resin (A). The polyester resin (A) has two or more ester bonds in its molecule.

聚酯樹脂(A)之HLB為4~18，於30℃之黏度為10~1,000,000Pa‧s。 The polyester resin (A) has an HLB of 4 to 18 and a viscosity of 10 to 1,000,000 Pa‧s at 30 °C.

於本說明書中，HLB係藉由格里芬(Griffin)之方法而求出之值。聚酯樹脂(A)之HLB為4~18，較佳為5~17，進而較佳為6~16。 In the present specification, HLB is obtained by the method of Griffin. The HLB of the polyester resin (A) is 4 to 18, preferably 5 to 17, more preferably 6 to 16.

於HLB未達4或超過18之情形時，由於纖維束之起毛增多，故而複合材料之強度降低。 When the HLB is less than 4 or exceeds 18, the strength of the composite material is lowered due to an increase in the fuzz of the fiber bundle.

聚酯樹脂(A)之30℃下之黏度為10~1,000,000Pa‧s，較佳為20~500,000Pa‧s，進而較佳為50~100,000Pa‧s。 The viscosity of the polyester resin (A) at 30 ° C is 10 to 1,000,000 Pa‧s, preferably 20 to 500,000 Pa‧s, and more preferably 50 to 100,000 Pa‧s.

於黏度未達10Pa‧s之情形時，纖維束之起毛增多，若黏度超過1,000,000Pa‧s，則纖維束之集束性變得過高，而開纖性惡化。 When the viscosity is less than 10 Pa‧s, the fuzz of the fiber bundle is increased, and if the viscosity exceeds 1,000,000 Pa‧s, the bundle property of the fiber bundle becomes too high, and the fiber opening property is deteriorated.

<聚酯樹脂之黏度之測定方法> <Method for Measuring Viscosity of Polyester Resin>

於本說明書中，聚酯樹脂(A)之黏度為複數黏度，例如可利用黏彈性測定裝置(例如Rheometric Scientific公司製造之ARES)進行測定。 In the present specification, the viscosity of the polyester resin (A) is a complex viscosity, and can be measured, for example, by a viscoelasticity measuring apparatus (for example, ARES manufactured by Rheometric Scientific Co., Ltd.).

將測定條件示於以下。 The measurement conditions are shown below.

樣品固定夾具：直徑25mm圓盤 Sample fixing fixture: 25mm diameter disc

間隙間距離：0.25mm Distance between gaps: 0.25mm

應變：1% Strain: 1%

頻率：1Hz Frequency: 1Hz

溫度：30℃ Temperature: 30 ° C

聚酯樹脂(A)中之酯基濃度基於上述聚酯樹脂(A)之重量，較佳為10mmol/g以下，進而較佳為5mmol/g以下。若酯基濃度過高，則聚酯樹脂(A)之黏度會增高，而抑制纖維束之起毛產生之效果降低。 The ester group concentration in the polyester resin (A) is preferably 10 mmol/g or less, and more preferably 5 mmol/g or less, based on the weight of the polyester resin (A). If the ester group concentration is too high, the viscosity of the polyester resin (A) is increased, and the effect of suppressing the occurrence of fuzzing of the fiber bundle is lowered.

聚酯樹脂(A)中之酯基濃度之下限並無特別限定，較佳為基於上述聚酯樹脂(A)之重量而為0.5mmol/g以上。 The lower limit of the ester group concentration in the polyester resin (A) is not particularly limited, but is preferably 0.5 mmol/g or more based on the weight of the polyester resin (A).

上述酯基濃度例如可藉由NMR(Nuclear Magnetic Resonance)測定而求出。 The ester group concentration can be determined, for example, by NMR (Nuclear Magnetic Resonance) measurement.

聚酯樹脂(A)較佳為二羧酸(a1)及/或二羧酸之酸酐(a2)、與二醇(b)之縮聚合物。 The polyester resin (A) is preferably a polycondensate of a dicarboxylic acid (a1) and/or a dicarboxylic acid anhydride (a2) and a diol (b).

作為二羧酸(a1)，可列舉：鏈式飽和二羧酸、鏈式不飽和二羧酸、脂環式二羧酸、二聚物酸及芳香族二羧酸等。 Examples of the dicarboxylic acid (a1) include a chain saturated dicarboxylic acid, a chain unsaturated dicarboxylic acid, an alicyclic dicarboxylic acid, a dimer acid, and an aromatic dicarboxylic acid.

作為鏈式飽和二羧酸，可列舉：碳數2~22之直鏈或支鏈之鏈式飽和二羧酸(草酸、丙二酸、琥珀酸、戊二酸、甲基琥珀酸、乙基琥珀酸、二甲基丙二酸、α-甲基戊二酸、β-甲基戊二酸、2,4-二乙基戊二酸、異丙基丙二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、癸烷二羧酸、十一烷二羧酸、十二烷二羧酸、十三烷二羧酸、十四烷二羧酸、十六烷二羧酸、十八烷二羧酸、二十烷二羧酸、癸基琥珀酸、十二烷基琥珀酸及十八烷基琥珀酸等)等。 The chain saturated dicarboxylic acid may, for example, be a linear or branched chain saturated dicarboxylic acid having 2 to 22 carbon atoms (oxalic acid, malonic acid, succinic acid, glutaric acid, methyl succinic acid, ethyl group). Succinic acid, dimethylmalonic acid, α-methylglutaric acid, β-methylglutaric acid, 2,4-diethylglutaric acid, isopropylmalonic acid, adipic acid, heptane Acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, sixteen An alkanedicarboxylic acid, octadecanedicarboxylic acid, eicosanedicarboxylic acid, decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid, etc.).

作為鏈式不飽和二羧酸，可列舉：碳數4~22之直鏈或支鏈之鏈式不飽和二羧酸(順丁烯二酸、反丁烯二酸、檸康酸、甲基反丁烯二酸、十二烯基琥珀酸、十五烯基琥珀酸及十八烯基琥珀酸等)等。 The chain unsaturated dicarboxylic acid may, for example, be a linear or branched chain unsaturated dicarboxylic acid having 4 to 22 carbon atoms (maleic acid, fumaric acid, citraconic acid, methyl group). Fumaric acid, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.).

作為脂環式二羧酸，可列舉：碳數7~14之脂環式二羧酸(1,3-或1,2-環戊烷二羧酸、1,2-、1,3-或1,4-環己烷二羧酸、1,2-、1,3-或1,4-環己烷二乙酸及二環己基-4,4'-二羧酸等)等。 Examples of the alicyclic dicarboxylic acid include an alicyclic dicarboxylic acid having a carbon number of 7 to 14 (1,3- or 1,2-cyclopentanedicarboxylic acid, 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid, 1,2-, 1,3- or 1,4-cyclohexanediacetic acid, dicyclohexyl-4,4'-dicarboxylic acid, etc.).

作為二聚物酸，可列舉碳數8~24之鏈式不飽和羧酸(油酸、亞麻油酸及次亞麻油酸等)之二聚物等。 Examples of the dimer acid include a dimer of a chain unsaturated carboxylic acid having 8 to 24 carbon atoms (such as oleic acid, linoleic acid, and linoleic acid).

作為芳香族二羧酸，可列舉：碳數8~14之芳香族二羧酸(對苯二甲酸、間苯二甲酸、鄰苯二甲酸、苯基丙二酸、苯基琥珀酸、β-苯基戊二酸、α-苯基己二酸、β-苯基己二酸、聯苯-2,2'-及4,4'-二羧酸、萘 二羧酸、5-磺基間苯二甲酸鈉及5-磺基間苯二甲酸鉀等)等。 Examples of the aromatic dicarboxylic acid include aromatic dicarboxylic acids having 8 to 14 carbon atoms (terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, phenylsuccinic acid, β-). Phenylglutaric acid, α-phenyladipate, β-phenyladipate, biphenyl-2,2'- and 4,4'-dicarboxylic acid, naphthalene Dicarboxylic acid, sodium 5-sulfoisophthalate, potassium 5-sulfoisophthalate, etc.).

作為二羧酸之酸酐(a2)，可列舉上述二羧酸(a1)之酸酐、例如琥珀酸酐、順丁烯二酸酐及鄰苯二甲酸酐等。 The acid anhydride (a2) of the dicarboxylic acid may, for example, be an acid anhydride of the above dicarboxylic acid (a1), for example, succinic anhydride, maleic anhydride or phthalic anhydride.

二羧酸(a1)及二羧酸之酸酐(a2)可單獨使用亦可併用2種以上。該等之中，就集束性之觀點而言，較佳為鏈式飽和二羧酸、鏈式不飽和二羧酸及芳香族二羧酸，進而較佳為草酸、丙二酸、琥珀酸、己二酸、癸二酸、順丁烯二酸、反丁烯二酸、對苯二甲酸、間苯二甲酸、鄰苯二甲酸及該等中之2種以上之併用，尤佳為己二酸、順丁烯二酸、反丁烯二酸、對苯二甲酸、間苯二甲酸及該等中之2種以上之併用。 The acid anhydride (a2) of the dicarboxylic acid (a1) and the dicarboxylic acid may be used singly or in combination of two or more. Among these, from the viewpoint of the bundling property, a chain saturated dicarboxylic acid, a chain unsaturated dicarboxylic acid, and an aromatic dicarboxylic acid are preferable, and oxalic acid, malonic acid, succinic acid, and the like are further preferable. Adipic acid, sebacic acid, maleic acid, fumaric acid, terephthalic acid, isophthalic acid, phthalic acid, and the combination of two or more of them, especially Acid, maleic acid, fumaric acid, terephthalic acid, isophthalic acid, and a combination of two or more of them.

作為二醇(b)，可列舉：脂肪族烷烴二醇及其環氧烷(以下，簡稱為AO)加成物、脂環式二醇及其AO加成物、一級胺之AO加成物以及含芳香環之二元酚之AO加成物等。 Examples of the diol (b) include an aliphatic alkane diol, an alkylene oxide (hereinafter abbreviated as AO) adduct, an alicyclic diol and an AO adduct thereof, and an AO adduct of a primary amine. And an AO adduct of a dihydric phenol containing an aromatic ring.

作為脂肪族烷烴二醇，可列舉：碳數2~16者、例如乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、辛二醇、癸烷二醇、十二烷二醇、十六烷二醇、新戊二醇及2,2-二乙基-1,3-丙二醇等。作為脂肪族烷烴二醇之AO加成物，可列舉將碳數2~4之AO加成於上述二醇而成之化合物。作為碳數2~4之AO，可列舉：環氧乙烷(以下，簡稱為EO)、1,2-環氧丙烷(以下，簡稱為PO)、1,2-環氧丁烷及1,4-環氧丁烷(以下，簡稱為BO)等。該等AO可併用2種以上，併用2種以上之情形時之鍵結方式可為嵌段加成、無規加成及併用該等之任一種。每1分子脂肪族烷烴二醇之AO之加成莫耳數通常為1~120莫耳。 Examples of the aliphatic alkanediol include those having 2 to 16 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol. Octanediol, decanediol, dodecanediol, hexadecanediol, neopentyl glycol, and 2,2-diethyl-1,3-propanediol. The AO adduct of the aliphatic alkane diol may be a compound obtained by adding AO having 2 to 4 carbon atoms to the diol. Examples of the AO having a carbon number of 2 to 4 include ethylene oxide (hereinafter, abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide and 1, 4-butylene oxide (hereinafter, abbreviated as BO) or the like. These AOs may be used in combination of two or more kinds, and in the case of two or more types, the bonding method may be a block addition, a random addition, or a combination of any of them. The AO addition mole number per one molecule of the aliphatic alkane diol is usually from 1 to 120 moles.

作為脂環式二醇，可列舉碳數4~16者、例如1,4-環己二 醇、1,4-環己烷二甲醇及氫化雙酚A等。作為脂環式二醇之AO加成物，可列舉將碳數2~4之AO加成於上述二醇而成之化合物。 Examples of the alicyclic diol include those having 4 to 16 carbon atoms, for example, 1,4-cyclohexane. Alcohol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, and the like. Examples of the AO adduct of the alicyclic diol include a compound obtained by adding AO having 2 to 4 carbon atoms to the diol.

作為一級胺之AO加成物中之一級胺，可列舉碳數1~22之一級胺、例如甲基胺、乙基胺、丙基胺、丁基胺、辛基胺、癸基胺及十二烷基胺等。作為一級胺之AO加成物，可列舉將碳數2~4之AO加成於上述胺而成之化合物。 As a primary amine in the AO adduct of the primary amine, a monoamine having a carbon number of 1 to 22, such as methylamine, ethylamine, propylamine, butylamine, octylamine, decylamine and ten Dialkylamine and the like. The AO adduct of the primary amine may be a compound obtained by adding AO having 2 to 4 carbon atoms to the above amine.

作為含芳香環之二元酚之AO加成物中之含芳香環之二元酚，可列舉：雙酚A、雙酚S、甲酚及對苯二酚等。作為含芳香環之二元酚之AO加成物，可列舉將碳數2~4之AO加成於上述酚而成之化合物。 Examples of the aromatic phenol-containing dihydric phenol in the AO adduct of the aromatic phenol-containing dihydric phenol include bisphenol A, bisphenol S, cresol, and hydroquinone. The AO adduct of the aromatic phenol-containing dihydric phenol is a compound obtained by adding AO having 2 to 4 carbon atoms to the phenol.

二醇(b)之中，就集束劑之乳化穩定性之觀點而言，較佳為脂肪族烷烴二醇及其AO加成物、脂環式二醇之AO加成物、一級胺之AO加成物、含芳香環之二元酚之AO加成物以及該等之2種以上之併用，進而較佳為脂肪族烷烴二醇及其AO加成物、含芳香環之二元酚之AO加成物以及該等之2種以上之併用。 Among the diols (b), from the viewpoint of emulsion stability of the sizing agent, preferred are aliphatic alkane diols and AO adducts thereof, AO adducts of alicyclic diols, and AO of primary amines. An adduct, an AO adduct of an aromatic ring-containing dihydric phenol, and a combination of two or more of them, and further preferably an aliphatic alkane diol and an AO adduct thereof, and an aromatic ring-containing dihydric phenol. AO adducts and the combination of two or more of them.

又，就抑制纖維束之起毛及集束劑之乳化穩定性之觀點而言，所使用之二醇(b)中之至少1種較佳為具有平均5~200個氧乙烯基之二醇(b1)，二醇(b1)較佳為具有平均10~100個氧乙烯基之二醇。 Further, from the viewpoint of suppressing fuzzing of the fiber bundle and emulsion stability of the sizing agent, at least one of the diols (b) used is preferably a diol having an average of 5 to 200 oxyethylene groups (b1) The diol (b1) is preferably a diol having an average of 10 to 100 oxyethylene groups.

藉由使用二醇(b1)，可抑制纖維束之起毛，發揮出優異之乳化穩定性。 By using the diol (b1), the fuzzing of the fiber bundle can be suppressed, and excellent emulsion stability can be exhibited.

作為具有平均5~200個氧乙烯基之二醇(b1)，可列舉上述中所例示之二醇(b)之中的下述者等。 Examples of the diol (b1) having an average of 5 to 200 oxyethylene groups include the following among the diols (b) exemplified above.

含芳香環之二元酚、一級胺或脂環式二醇之AO加成物之中，可列舉加成有平均5~200個EO者等。具體而言，可列舉：雙酚A之 EO 10莫耳加成物、雙酚A之EO 40莫耳加成物、雙酚A之EO 100莫耳加成物及雙酚A之EO 200莫耳加成物等。 Among the AO adducts of the aromatic phenol-containing dihydric phenol, the primary amine or the alicyclic diol, an average of 5 to 200 EO is added. Specifically, it can be mentioned that: bisphenol A EO 10 molar addition, EO 40 molar addition of bisphenol A, EO 100 molar addition of bisphenol A, and EO 200 molar addition of bisphenol A.

碳數3~4之脂肪族烷烴二醇之AO加成物之中，可列舉加成有平均5~200個EO者。具體而言，可列舉：丙二醇之EO 5莫耳加成物、丙二醇之PO 2莫耳/EO 20莫耳加成物(嵌段加成物)、丙二醇之PO 5莫耳/EO 100莫耳加成物(嵌段加成物)及丙二醇之PO 5莫耳/EO 100莫耳加成物(無規加成物)等。 Among the AO adducts of the aliphatic alkanediol having 3 to 4 carbon atoms, those having an average of 5 to 200 EO additions can be mentioned. Specific examples thereof include EO 5 molar addition of propylene glycol, PO 2 molar/EO 20 molar addition of propylene glycol (block addition product), and PO 5 mole/EO 100 mole of propylene glycol. Adduct (block adduct) and PO 5 molar/EO 100 molar addition of propylene glycol (random adduct).

乙二醇之AO加成物之中，可列舉EO之平均加成莫耳數為4~199莫耳者。具體而言，可列舉：乙二醇之EO 4莫耳加成物及乙二醇之EO 199莫耳加成物等聚乙二醇。 Among the AO adducts of ethylene glycol, the average addition molar amount of EO is 4 to 199 moles. Specific examples include polyethylene glycol such as EO 4 molar addition of ethylene glycol and EO 199 molar addition of ethylene glycol.

具有平均5~200個氧乙烯基之二醇(b1)之中，就抑制纖維束之起毛之觀點而言，較佳為雙酚A之EO加成物及/或乙二醇之EO加成物。 Among the diols (b1) having an average of 5 to 200 oxyethylene groups, the EO addition of the EO adduct of bisphenol A and/or ethylene glycol is preferred from the viewpoint of suppressing fuzzing of the fiber bundle. Things.

每1種二醇(b)之氧乙烯基之平均個數例如於可使二醇(b)自聚酯樹脂(A)單離之情形時，可藉由對二醇(b)進行NMR測定而求出。 The average number of oxyethylene groups per diol (b) can be determined by NMR measurement of the diol (b), for example, when the diol (b) can be isolated from the polyester resin (A). And find it.

於無法使二醇(b)自聚酯樹脂(A)單離(isolation)之情形時，例如可使聚酯樹脂(A)水解而以二醇混合物之形式獲得後，進而藉由分離凝膠滲透層析法(以下，稱為分離GPC)將二醇混合物區分，並對各區分成分進行NMR測定而鑑定結構，藉此算出上述氧乙烯基之平均個數。 In the case where the diol (b) cannot be isolated from the polyester resin (A), for example, the polyester resin (A) can be hydrolyzed to be obtained as a diol mixture, and then the gel can be separated. Permeation chromatography (hereinafter referred to as separation of GPC) distinguishes the diol mixture, and NMR measurement of each component is carried out to identify the structure, thereby calculating the average number of oxyethylene groups.

分離GPC之測定條件例如如下所述。 The measurement conditions for separating GPC are as follows, for example.

機型：LC-09(日本分析工業(股份有限公司)製造) Model: LC-09 (manufactured by Nippon Analytical Industries Co., Ltd.)

管柱：JAIGEL-3H Column: JAIGEL-3H

+JAIGEL-2H +JAIGEL-2H

+JAIGEL-1H +JAIGEL-1H

管柱溫度：25℃ Column temperature: 25 ° C

溶劑：氯仿 Solvent: chloroform

流速：3ml/min Flow rate: 3ml/min

試樣濃度：2重量% Sample concentration: 2% by weight

注入量：3ml Injection volume: 3ml

作為製造聚酯樹脂(A)之方法，例如可列舉：以特定莫耳比添加二羧酸(a1)及/或二羧酸之酸酐(a2)與二醇(b)，並於反應溫度100~250℃、壓力-0.1~1.2MPa、於攪拌下，將水蒸餾去除之方法。亦可於反應混合物中進而添加二醇(b)而使之反應。 As a method of producing the polyester resin (A), for example, an acid anhydride (a2) and a diol (b) of a dicarboxylic acid (a1) and/or a dicarboxylic acid are added at a specific molar ratio, and the reaction temperature is 100. ~250 ° C, pressure -0.1 ~ 1.2MPa, the method of distillation of water under stirring. Further, the diol (b) may be further added to the reaction mixture to cause a reaction.

於製造聚酯樹脂(A)時，較佳為基於聚酯樹脂(A)之重量添加0.05~0.5重量%之觸媒。作為觸媒，例如可列舉：對甲苯磺酸、二丁基氧化錫、鈦酸四異丙氧酯及草酸鈦酸鉀，就反應性及對環境之影響之觀點而言，較佳為鈦酸四異丙氧酯及草酸鈦酸鉀，進而較佳為草酸鈦酸鉀。 In the production of the polyester resin (A), it is preferred to add 0.05 to 0.5% by weight of a catalyst based on the weight of the polyester resin (A). Examples of the catalyst include p-toluenesulfonic acid, dibutyltin oxide, tetraisopropoxy titanate, and potassium oxalate titanate. From the viewpoint of reactivity and environmental influence, titanic acid is preferred. Tetrapropoxylate and potassium oxalate titanate are further preferably potassium oxalate titanate.

本發明之纖維用集束劑組成物係含有反應性化合物(B)而成。 The sizing agent composition for fibers of the present invention contains a reactive compound (B).

反應性化合物(B)為選自由封端異氰酸酯、三級胺、三級胺鹽、四級銨鹽、四級鏻鹽及膦化合物所組成之群中之至少1種。 The reactive compound (B) is at least one selected from the group consisting of a blocked isocyanate, a tertiary amine, a tertiary amine salt, a quaternary ammonium salt, a quaternary phosphonium salt, and a phosphine compound.

所謂封端異氰酸酯係利用封端化劑對異氰酸酯化合物之異氰酸酯基(-NCO)進行封阻而成之化合物。此種封端異氰酸酯可抑制異氰酸酯基之反應性，並藉由加熱使封端化劑解離，藉此異氰酸酯基之反應 性恢復。 The blocked isocyanate is a compound obtained by blocking an isocyanate group (-NCO) of an isocyanate compound with a blocking agent. The blocked isocyanate inhibits the reactivity of the isocyanate group and dissociates the blocking agent by heating, whereby the reaction of the isocyanate group Sexual recovery.

作為異氰酸酯化合物，可列舉：脂肪族異氰酸酯、脂環式異氰酸酯、芳香脂肪族異氰酸酯、芳香族異氰酸酯及聚異氰酸酯之改質體等。 Examples of the isocyanate compound include aliphatic isocyanate, alicyclic isocyanate, aromatic aliphatic isocyanate, aromatic isocyanate, and polyisocyanate modified body.

作為脂肪族異氰酸酯，可列舉：異氰酸十八烷基酯、伸乙基二異氰酸酯、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯(HDI)、七亞甲基二異氰酸酯、八亞甲基二異氰酸酯、十亞甲基二異氰酸酯、十二亞甲基二異氰酸酯、2,2,4-或2,4,4-三甲基六亞甲基二異氰酸酯、離胺酸二異氰酸酯、2,6-二異氰酸酯基己酸甲酯(2,6-diisocyanate methyl caproate)、2,6-二異氰酸酯基己酸乙酯、反丁烯二酸雙(2-異氰酸酯基乙基)酯、碳酸雙(2-異氰酸酯基乙基)酯、1,6,11-十一烷三異氰酸酯、1,8-二異氰酸酯基-4-異氰酸酯基甲基辛烷、1,3,6-六亞甲基三異氰酸酯、離胺酸酯三異氰酸酯(離胺酸與烷醇胺之反應產物之碳醯氯化物)、2-異氰酸酯基乙基-2,6-二異氰酸酯基己酸酯及2-或3-異氰酸酯基丙基-2,6-二異氰酸酯基己酸酯等。 Examples of the aliphatic isocyanate include octadecyl isocyanate, ethyl diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, and octadecylene. Diisocyanate, decamethyl diisocyanate, dodecamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, isocyanate diisocyanate, 2, 2,6-diisocyanate methyl caproate, 2,6-diisocyanate ethyl hexanoate, bis(2-isocyanateethyl) fumarate, bis (carbonate) 2-Iocyanate ethyl)ester, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate , amino acid triisocyanate (carbonium chloride of a reaction product of an amine acid and an alkanolamine), 2-isocyanate ethyl-2,6-diisocyanate hexanoate, and 2- or 3-isocyanate group Propyl-2,6-diisocyanate hexanoate and the like.

作為脂環式異氰酸酯，可列舉：異佛爾酮二異氰酸酯(IPDI)、二環己基甲烷-4,4'-二異氰酸酯(氫化MDI)、環伸己基二異氰酸酯、甲基環伸己基二異氰酸酯、雙(2-異氰酸酯基乙基)-4-伸環己基-1,2-二羧酸酯、2,5-或2,6-降莰烷二異氰酸酯及雙環庚烷三異氰酸酯等。 Examples of the alicyclic isocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexyl diisocyanate, and methylcyclohexyl diisocyanate. Bis(2-Isocyanateethyl)-4-cyclohexyl-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, bicycloheptane triisocyanate, and the like.

作為芳香脂肪族異氰酸酯，可列舉：間或對苯二甲基二異氰酸酯(XDI)、二乙基苯二異氰酸酯及α,α,α',α'-四甲基苯二甲基二異氰酸酯(TMXDI)等。 Examples of the aromatic aliphatic isocyanate include m- or p-xylylene diisocyanate (XDI), diethylbenzene diisocyanate, and α,α,α',α'-tetramethylbenzenedimethyl diisocyanate (TMXDI). )Wait.

作為芳香族異氰酸酯，可列舉：1,3-或1,4-苯二異氰酸酯、 2,4-或2,6-甲苯二異氰酸酯(TDI)、4,4'-或2,4'-二苯基甲烷二異氰酸酯(MDI)、間或對異氰酸酯基苯基磺醯基異氰酸酯、4,4'-二異氰酸酯基聯苯、3,3'-二甲基-4,4'-二異氰酸酯基聯苯、3,3'-二甲基-4,4'-二異氰酸酯基二苯基甲烷、1,5-萘二異氰酸酯、粗製TDI及粗製MDI(聚亞甲基聚苯基聚異氰酸酯)等。 Examples of the aromatic isocyanate include 1,3- or 1,4-phenyldiisocyanate. 2,4- or 2,6-toluene diisocyanate (TDI), 4,4'- or 2,4'-diphenylmethane diisocyanate (MDI), m- or p-isocyanate phenylsulfonyl isocyanate, 4 , 4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate diphenyl Methane, 1,5-naphthalene diisocyanate, crude TDI, and crude MDI (polymethylene polyphenyl polyisocyanate).

作為聚異氰酸酯之改質體，可列舉：MDI、TDI、HDI及IPDI等胺酯(urethane)改質物(使多元醇與過量之聚異氰酸酯反應而獲得之異氰酸酯末端胺酯預聚物)、或使該等聚異氰酸酯與具有活性氫原子之化合物(例如三羥甲基丙烷、新戊四醇等)以異氰酸酯基(-NCO)與羥基(-OH)之比超過1的莫耳比進行反應而獲得之含末端異氰酸酯基之多元醇加成聚異氰酸酯等。 Examples of the modified polyisocyanate include an urethane modified product such as MDI, TDI, HDI, and IPDI (isocyanate terminal amine ester prepolymer obtained by reacting a polyhydric alcohol with an excess of polyisocyanate), or The polyisocyanate is reacted with a compound having an active hydrogen atom (for example, trimethylolpropane, neopentyl alcohol, etc.) in a molar ratio of an isocyanate group (-NCO) to a hydroxyl group (-OH) of more than 1 to obtain The polyisocyanate containing a terminal isocyanate group is added to a polyisocyanate or the like.

該等異氰酸酯化合物之中，就纖維束之集束性之觀點而言，較佳為芳香脂肪族異氰酸酯及芳香族異氰酸酯，進而較佳為芳香族異氰酸酯。具體而言為XDI、TDI、MDI等。 Among these isocyanate compounds, from the viewpoint of the bundle property of the fiber bundle, an aromatic aliphatic isocyanate and an aromatic isocyanate are preferable, and an aromatic isocyanate is further preferable. Specifically, it is XDI, TDI, MDI, and the like.

作為封端化劑，並無特別限定，具體而言，可列舉：內醯胺(ε-己內醯胺、δ-戊內醯胺、γ-丁內醯胺等)、酚(苯酚、甲酚、乙基苯酚、丁基苯酚、壬基苯酚、二壬基苯酚等)、肟(甲基乙基酮肟、苯乙酮肟、二苯甲酮肟等)、醇(甲醇、乙醇、丁醇、環己醇等)、活性亞甲基(丙二酸二甲酯、丙二酸二乙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯丙酮等)、硫醇(丁基硫醇、十二烷基硫醇等)、醯胺(乙醯苯胺、乙醯胺等)、醯亞胺(琥珀醯亞胺、順丁烯二醯亞胺等)、亞硫酸鹽(重亞硫酸鈉等)、溶纖素(甲基溶纖素、乙基溶纖素、丁基溶纖素及己基溶纖素等)、吡唑(吡 唑、3,5-二甲基吡唑、3-甲基吡唑、4-苄基-3,5-二甲基吡唑、4-硝基-3,5-二甲基吡唑、4-溴-3,5-二甲基吡唑及3-甲基-5-苯基吡唑等)、胺(二甲基胺、二乙基胺、二正丙基胺、二環己基胺、二苯基胺、二甲苯胺、N,N-二乙基羥基胺、2-羥基吡啶及2-巰基吡啶等)及***等。亦可使用該等之2種以上之混合物等。 The blocking agent is not particularly limited, and specific examples thereof include indoleamine (ε-caprolactam, δ-valeroinamide, γ-butyrolactam, etc.), and phenol (phenol, A). Phenol, ethyl phenol, butyl phenol, nonyl phenol, dinonyl phenol, etc.), hydrazine (methyl ethyl ketone oxime, acetophenone oxime, benzophenone oxime, etc.), alcohol (methanol, ethanol, butyl) Alcohol, cyclohexanol, etc.), active methylene (dimethyl dimethyl malon, diethyl malonate, methyl acetonitrile, ethyl acetate, acetonitrile, etc.), thiol (butyl Mercaptan, dodecyl mercaptan, etc.), decylamine (acetanilide, acetamide, etc.), quinone imine (ammonium imide, maleimide, etc.), sulfite (sodium bisulfite) Etc.), cellulolytic (methyl cellosolve, ethyl cellosolve, butyl cellosolve and hexyl cellosolve, etc.), pyrazole (pyridyl Oxazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4 -Bromo-3,5-dimethylpyrazole and 3-methyl-5-phenylpyrazole, etc.), amine (dimethylamine, diethylamine, di-n-propylamine, dicyclohexylamine, Diphenylamine, xylyleneamine, N,N-diethylhydroxylamine, 2-hydroxypyridine, 2-mercaptopyridine, etc.) and triazole. A mixture of two or more of these may be used.

該等封端化劑之中，就複合材料之拉伸強度之觀點而言，較佳為醇、酚、活性亞甲基、肟、內醯胺、胺及該等之混合物，進而較佳為肟、吡唑、胺、***及該等之混合物，尤佳為胺。 Among these blocking agents, from the viewpoint of the tensile strength of the composite material, an alcohol, a phenol, an active methylene group, an anthracene, an indoleamine, an amine, and a mixture thereof are preferable, and further preferably Anthracene, pyrazole, amine, triazole and mixtures thereof are preferred as amines.

作為封端異氰酸酯之市售品，可列舉：DM-6400、Meikanate DM-3031CONC、Meikanate DM-35HC、Meikanate TP-10、Meikanate CX、SU-268A、NBP-8730、NBP-211[明成化學工業(股份有限公司)製造]、Elastron BN-69、BN-44、BN-04、BN-08[第一工業製藥股份有限公司製造]、Takenate WB-700、WB-770、WB-920[Mitsui Chemicals Polyurethanes股份有限公司製造]、Karenz MOI-BM、MOI-BP[昭和電工股份有限公司製造]、Duranate MF-K60B、SBN-70D、MF-B60B、MF-B90B、17B-60P、TPA-B80B、TPA-B80E、E402-B80B[Asahi Kasei Chemicals股份有限公司製造]、BI-7950、BI-7951、BI-7960、BI-7961、BI-7963、BI-7982、BI-7991、BI-7992[Baxenden股份有限公司製造]、IPDI-B1065、IPDI-B1530、IPDI-BF1540[HULS股份有限公司製造]、BURNOCK B7-887-60、B3-867、DB980K[大日本油墨股份有限公司製造]、Desmodur BL1100/1、Sumidur BL3175、Desmodur BL3272MPA、Desmodur BL3475BA/SN、Desmodur BL3575/1MPA/SN[Sumitomo Bayer Urethane股份有限公司製造]及3-(3,4-二氯 苯基)-1,1-二甲基脲「DCMU」[保土谷化學(股份有限公司)製造]等。 As a commercially available product of blocked isocyanate, DM-6400, Meikanate DM-3031CONC, Meikanate DM-35HC, Meikanate TP-10, Meikanate CX, SU-268A, NBP-8730, NBP-211 (Mingcheng Chemical Industry Co., Ltd.) Co., Ltd.) Manufacturing], Elastron BN-69, BN-44, BN-04, BN-08 [Manufactured by Daiichi Kogyo Co., Ltd.], Takenate WB-700, WB-770, WB-920 [Mitsui Chemicals Polyurethanes Manufacturing Co., Ltd.], Karenz MOI-BM, MOI-BP [Manufactured by Showa Denko Co., Ltd.], Duranate MF-K60B, SBN-70D, MF-B60B, MF-B90B, 17B-60P, TPA-B80B, TPA- B80E, E402-B80B [manufactured by Asahi Kasei Chemicals Co., Ltd.], BI-7950, BI-7951, BI-7960, BI-7961, BI-7963, BI-7982, BI-7991, BI-7992 [Baxenden shares limited Manufactured by the company], IPDI-B1065, IPDI-B1530, IPDI-BF1540 [manufactured by HULS Co., Ltd.], BURNOCK B7-887-60, B3-867, DB980K [manufactured by Dainippon Ink Co., Ltd.], Desmodur BL1100/1, Sumidur BL3175, Desmodur BL3272MPA, Desmodur BL3475BA/SN, Desmodur BL3575/1MPA/SN [Sumitomo Bayer Urethane Limited Share Manufacturing Division] and 3- (3,4-Dichloro Phenyl)-1,1-dimethylurea "DCMU" [manufactured by Hodogaya Chemical Co., Ltd.].

作為三級胺，可列舉：脂肪族胺、芳香族胺、一級胺或二級胺之AO加成物、含氮雜環式脂肪族胺、具有咪唑啉環之化合物及咪唑同系物等。 Examples of the tertiary amine include an aliphatic amine, an aromatic amine, an AO adduct of a primary or secondary amine, a nitrogen-containing heterocyclic aliphatic amine, a compound having an imidazoline ring, and an imidazole homolog.

作為脂肪族胺，可列舉：烷基胺(三甲基胺、三乙基胺、乙基二甲基胺、三異丙基胺、三丁基胺、三辛基胺、二乙基異丙基胺、四甲基乙二胺、二異丙基乙基胺等)、烷醇胺(二丁基單乙醇胺、N-乙基二乙醇胺、三乙醇胺、三異丙醇胺等)等。 As the aliphatic amine, an alkylamine (trimethylamine, triethylamine, ethyldimethylamine, triisopropylamine, tributylamine, trioctylamine, diethylisopropyl) may be mentioned. Alkylamine, tetramethylethylenediamine, diisopropylethylamine, etc.), alkanolamine (dibutylmonoethanolamine, N-ethyldiethanolamine, triethanolamine, triisopropanolamine, etc.).

作為芳香族胺，可列舉：2,4,6-三(二甲基胺基甲基)苯酚、1,8-雙(二甲基胺基)萘等。 Examples of the aromatic amine include 2,4,6-tris(dimethylaminomethyl)phenol and 1,8-bis(dimethylamino)naphthalene.

作為一級胺或二級胺之AO加成物，可列舉：丁基胺之EO 4莫耳加成物、丁基胺之EO 10莫耳加成物、丁基胺之PO 10莫耳加成物、月桂胺之EO 10莫耳加成物、硬脂胺之EO 10莫耳加成物、硬脂胺之EO 15莫耳加成物、環己基胺之EO 2莫耳加成物、苯胺之EO 2莫耳加成物、六亞甲基二胺之EO 4莫耳加成物、二乙基胺之EO 4莫耳加成物、二乙基胺之PO 10莫耳加成物、二丁基胺之EO 4莫耳加成物、二丁基胺之PO 10莫耳加成物、月桂基甲基胺之EO 10莫耳加成物、甲基硬脂胺之EO 15莫耳加成物及甲基硬脂胺之PO 10莫耳加成物等。 Examples of the AO adduct of the primary or secondary amine include EO 4 molar addition of butylamine, EO 10 molar addition of butylamine, and PO 10 molar addition of butylamine. EO 10 molar addition of laurylamine, EO 10 molar addition of stearylamine, EO 15 molar addition of stearylamine, EO 2 molar addition of cyclohexylamine, aniline EO 2 molar addition, EO 4 molar addition of hexamethylenediamine, EO 4 molar addition of diethylamine, PO 10 molar addition of diethylamine, EO 4 molar addition of dibutylamine, PO 10 molar addition of dibutylamine, EO 10 molar addition of lauryl methylamine, EO 15 mole of methyl stearylamine The addition product and the PO 10 molar addition of methyl stearylamine and the like.

作為含氮雜環式脂肪族胺，可列舉：N-甲基吡咯啶、N-乙基吡咯啶、N-甲基哌啶、N-乙基哌啶、N-丁基哌啶、N-甲基六亞甲基亞胺、N-乙基六亞甲基亞胺、N-甲基嗎福啉、N-丁基嗎福啉、N,N'-二甲基哌、N,N'-二乙基哌、2,6-二甲吡啶、1-甲基-1,4,5,6-四氫嘧啶、1,2-二 甲基-1,4,5,6-四氫嘧啶、1,5-二氮雜雙環[4.3.0]-5-壬烯(DBN)、1,8-二氮雜雙環[5.4.0]-7-十一烯(DBU)、吡啶、4-二甲基胺基吡啶、甲吡啶類、喹啉、2,2'-聯吡啶等。 Examples of the nitrogen-containing heterocyclic aliphatic amine include N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-butylpiperidine, and N- Methylhexamethyleneimine, N-ethylhexamethyleneimine, N-methylmorpholine, N-butylmorpholine, N,N'-dimethylperazine , N, N'-diethyl pipe , 2,6-Dipyridyl, 1-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,5- Diazabicyclo[4.3.0]-5-decene (DBN), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), pyridine, 4-dimethylamino group Pyridine, pyridyl, quinoline, 2,2'-bipyridyl and the like.

作為具有咪唑啉環之化合物，可列舉：1,2-二甲基咪唑啉,1,2,4-三甲基咪唑啉、1,2,5-三甲基咪唑啉、1,4-二甲基-2-乙基咪唑啉、1-甲基-2-乙基咪唑啉、1-甲基-2-庚基咪唑啉、1-甲基-2-(4'-庚基)咪唑啉、1-甲基-2-十二烷基咪唑啉等。 Examples of the compound having an imidazoline ring include 1,2-dimethylimidazoline, 1,2,4-trimethylimidazoline, 1,2,5-trimethylimidazoline, and 1,4-di Methyl-2-ethylimidazoline, 1-methyl-2-ethylimidazoline, 1-methyl-2-heptyl imidazoline, 1-methyl-2-(4'-heptyl) imidazoline , 1-methyl-2-dodecylimidazoline, and the like.

作為咪唑同系物，可列舉：1-甲基咪唑、1-乙基咪唑、1-乙基-2-甲基咪唑、1,2-二甲基咪唑、1-甲基-2-乙基咪唑、1,4-二甲基咪唑、1,5-二甲基咪唑、1,2,4-三甲基咪唑、1,4-二甲基-2-乙基咪唑等。 Examples of the imidazole homologues include 1-methylimidazole, 1-ethylimidazole, 1-ethyl-2-methylimidazole, 1,2-dimethylimidazole, and 1-methyl-2-ethylimidazole. , 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,4-trimethylimidazole, 1,4-dimethyl-2-ethylimidazole, and the like.

該等三級胺之中，就複合材料之強度之觀點而言，較佳為脂肪族胺、芳香族胺、一級胺或二級胺之AO加成物及含氮雜環式脂肪族胺，進而較佳為三異丙基胺、二異丙基乙基胺、二丁基乙醇胺、二乙基乙醇胺、三乙醇胺、三異丙醇胺、2,4,6-三(二甲基胺基甲基)苯酚、1,8-雙(二甲基胺基)萘、2,6-二甲吡啶、DBU及DBN。 Among the tertiary amines, from the viewpoint of the strength of the composite material, an AO adduct of an aliphatic amine, an aromatic amine, a primary or secondary amine, and a nitrogen-containing heterocyclic aliphatic amine are preferred. Further preferred are triisopropylamine, diisopropylethylamine, dibutylethanolamine, diethylethanolamine, triethanolamine, triisopropanolamine, 2,4,6-tris(dimethylamino) Methyl)phenol, 1,8-bis(dimethylamino)naphthalene, 2,6-dimethylpyridine, DBU and DBN.

作為三級胺鹽，可列舉：上述三級胺之無機酸(硫酸、鹽酸、硝酸、磷酸等)鹽、有機酸(羧酸、磺酸、酚類等)鹽。該等鹽可藉由將上述三級胺中和、或使相當之二級胺與烷基化劑[二烷基硫酸(例如二甲基硫酸等)、烷基鹵化物(例如氯甲烷等)]反應而製造。 Examples of the tertiary amine salt include salts of inorganic acids (sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc.) and salts of organic acids (carboxylic acids, sulfonic acids, phenols, and the like). The salts may be neutralized by the above tertiary amines, or equivalent secondary amines with alkylating agents [dialkylsulfuric acid (eg, dimethylsulfuric acid, etc.), alkyl halides (eg, methyl chloride, etc.) ] Produced by reaction.

作為上述羧酸，可列舉：脂肪族羧酸、脂環式羧酸及芳香族羧酸等。 Examples of the carboxylic acid include an aliphatic carboxylic acid, an alicyclic carboxylic acid, and an aromatic carboxylic acid.

作為脂肪族羧酸，可列舉：單羧酸(碳數1~30，例如甲酸、乙酸、辛 酸、油酸等)；聚羧酸[二羧酸(碳數2~30，例如草酸、丙二酸、琥珀酸、戊二酸、己二酸、辛二酸、癸二酸、反丁烯二酸、順丁烯二酸等)、三羧酸(碳數3~30，例如檸檬酸等)、4元以上之聚羧酸(碳數4~30，例如EDTA等)]。 Examples of the aliphatic carboxylic acid include monocarboxylic acids (carbon number 1 to 30, such as formic acid, acetic acid, and octane). Acid, oleic acid, etc.; polycarboxylic acid [dicarboxylic acid (carbon number 2 ~ 30, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, anti-butene A dicarboxylic acid (such as citric acid or the like), a tricarboxylic acid (having a carbon number of 3 to 30, for example, citric acid), or a polyvalent carboxylic acid having 4 or more members (having a carbon number of 4 to 30, for example, EDTA or the like).

作為脂環式羧酸，可列舉：單羧酸(碳數4~30，例如環己烷羧酸等)；二羧酸(碳數5~30，例如1,2-環己烷二羧酸等)等。 Examples of the alicyclic carboxylic acid include a monocarboxylic acid (having a carbon number of 4 to 30, for example, a cyclohexanecarboxylic acid); and a dicarboxylic acid (having a carbon number of 5 to 30, for example, 1,2-cyclohexanedicarboxylic acid) and many more.

作為芳香族羧酸，可列舉：單羧酸(碳數7~50，例如苯甲酸等)；聚羧酸[二羧酸(碳數7~50，例如鄰苯二甲酸、對苯二甲酸、間苯二甲酸等)、三羧酸(碳數8~50，例如1,2,4-苯三甲酸(trimellitic acid)等)、4元以上之聚羧酸(碳數9~50，例如1,2,4,5-苯四甲酸(pyromellitic acid)等)]。 Examples of the aromatic carboxylic acid include a monocarboxylic acid (carbon number: 7 to 50, for example, benzoic acid); and a polycarboxylic acid [dicarboxylic acid (carbon number: 7 to 50, such as phthalic acid, terephthalic acid, Tricarboxylic acid (such as triethyl carboxylic acid (carbon number 8 to 50, such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), etc.), or more than 4 or more polycarboxylic acids (carbon number 9 to 50, for example, 1 , 2,4,5-benzenetetracarboxylic acid (pyromellitic acid, etc.)].

作為上述磺酸，可列舉：脂肪族磺酸(碳數1~20，例如甲磺酸、乙磺酸等)及芳香族磺酸(碳數6~50，例如苯磺酸、甲苯磺酸、萘磺酸等)。 Examples of the sulfonic acid include aliphatic sulfonic acids (carbon number 1 to 20, such as methanesulfonic acid, ethanesulfonic acid, etc.) and aromatic sulfonic acids (carbon numbers 6 to 50, such as benzenesulfonic acid, toluenesulfonic acid, Naphthalenesulfonic acid, etc.).

作為上述酚類，可列舉單環酚(碳數6~30)及多環酚(碳數10~50)，分別可列舉一元酚及多酚。作為單環之一元酚，可列舉：苯酚、甲酚、二甲苯酚、香芹酚、瑞香草酚等，作為單環之多酚，可列舉：鄰苯二酚、間苯二酚、對苯二酚、鄰苯三酚、間苯三酚等。作為多環之一元酚，可列舉萘酚等，作為多環之多酚，可列舉二羥基蒽酚等。 Examples of the phenols include monocyclic phenols (carbon number 6 to 30) and polycyclic phenols (carbon numbers 10 to 50), and examples thereof include monohydric phenols and polyphenols. Examples of the monocyclic monohydric phenol include phenol, cresol, xylenol, carvacrol, and thymol, and examples of the monocyclic polyphenol include catechol, resorcin, and benzene. Diphenol, pyrogallol, phloroglucinol and the like. Examples of the polycyclic monohydric phenol include naphthol and the like, and examples of the polycyclic polyphenol include dihydroxy decylphenol.

三級胺鹽之中，就複合材料之強度之觀點而言，較佳為DBU鹽及DBN鹽，作為DBU鹽，具體而言，可列舉：DBU之酚鹽(例如U-CAT SA1，San-Apro(股份有限公司)製造)、DBU之辛酸鹽(例如U-CAT SA102，San-Apro(股份有限公司)製造)、DBU之對甲苯磺酸鹽(例 如U-CAT SA506，San-Apro(股份有限公司)製造)、DBU之甲酸鹽(例如U-CAT SA603，San-Apro(股份有限公司)製造)、DBU之鄰苯二甲酸鹽(例如U-CAT SA810，San-Apro(股份有限公司)製造)、及DBU之苯酚酚醛清漆(phenol novolac)樹脂鹽(例如U-CAT SA831、SA841、SA851、SA881，San-Apro(股份有限公司)製造)等。 Among the tertiary amine salts, from the viewpoint of the strength of the composite material, DBU salt and DBN salt are preferred, and as the DBU salt, specifically, a phenol salt of DBU (for example, U-CAT SA1, San-) is exemplified. Apro (manufactured by Apro Co., Ltd.), DBU octanoate (for example, U-CAT SA102, manufactured by San-Apro Co., Ltd.), DBU p-toluenesulfonate (example) For example, U-CAT SA506, manufactured by San-Apro Co., Ltd., DBU formate (for example, U-CAT SA603, manufactured by San-Apro Co., Ltd.), DBU phthalate (for example) U-CAT SA810, manufactured by San-Apro Co., Ltd., and phenol novolac resin salt of DBU (for example, U-CAT SA831, SA841, SA851, SA881, manufactured by San-Apro Co., Ltd.) )Wait.

四級銨鹽係由四級銨基與陰離子所構成，可藉由使任意三級胺與烷基化劑[二烷基硫酸(例如二甲基硫酸等)、烷基鹵化物(例如氯甲烷等)等]反應而製造。 The quaternary ammonium salt is composed of a quaternary ammonium group and an anion, and can be obtained by subjecting any tertiary amine to an alkylating agent [dialkylsulfuric acid (such as dimethylsulfuric acid), alkyl halide (such as methyl chloride). Manufactured by reaction, etc.].

作為四級銨基，可列舉：四烷基銨系化合物(四甲基銨、乙基三甲基銨、苄基三甲基銨等)、吡咯烷鎓(pyrrolidinium)系化合物(N,N-二甲基吡咯烷鎓、N-乙基-N-甲基吡咯烷鎓、N,N-二乙基吡咯烷鎓等)、哌啶鎓系化合物(N,N-二甲基哌啶鎓等)、六亞甲基亞胺系化合物(N,N-二甲基六亞甲基亞胺等)、嗎福啉鎓系化合物(N,N-二甲基嗎福啉鎓等)、哌鎓系化合物(N,N,N',N'-四甲基哌鎓等)、四氫嘧啶鎓系化合物(1,3-二甲基-1,4,5,6-四氫嘧啶鎓、1,2,3-三甲基-1,4,5,6-四氫嘧啶鎓、1,2,3,4-四甲基-1,4,5,6-四氫嘧啶鎓、1,2,3,5-四甲基-1,4,5,6-四氫嘧啶鎓、8-甲基-1,8-二氮雜雙環[5.4.0]-7-十一烯鎓、5-甲基-1,5-二氮雜雙環[4.3.0]-5-壬烯鎓、8-乙基-1,8-二氮雜雙環[5.4.0]-7-十一烯鎓、5-乙基-1,5-二氮雜雙環[4.3.0]-5-壬烯鎓等)、吡啶鎓系化合物(N-甲吡啶鎓等)、咪唑啉鎓系化合物(1,2,3-三甲基咪唑啉鎓、1-甲基-2,3,4-三乙基咪唑啉鎓、1,1,2,4,5-五甲基咪唑啉鎓等)、咪唑鎓系化合物(1,3-二甲基咪唑鎓、1-乙基-3-甲基咪唑鎓、1,2,3,4-四甲基咪唑鎓、 1,3,4-三甲基-2-乙基咪唑鎓、1,3-二甲基-2,4-二乙基咪唑鎓、1,1-二甲基-2-(4'-庚基)咪唑鎓、1,1-二甲基-2-十二烷基咪唑鎓、1,1-二甲基咪唑鎓、1,1,2,5-四甲基咪唑鎓、1,1,2,4,5-五甲基咪唑鎓等)、喹啉鎓系化合物(N-甲基喹啉鎓等)、聯吡啶鎓系化合物(N-甲基-2,2'-聯吡啶鎓等)。 Examples of the quaternary ammonium group include a tetraalkylammonium compound (tetramethylammonium, ethyltrimethylammonium, benzyltrimethylammonium, etc.) and a pyrrolidinium compound (N,N-). Dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, N,N-diethylpyrrolidinium, etc.), piperidinium compounds (N,N-dimethylpiperidinium, etc.) ), hexamethyleneimine-based compound (N,N-dimethylhexamethyleneimine, etc.), morpholinin-based compound (N,N-dimethylmorpholine oxime, etc.), piperazine Lanthanide compounds (N, N, N', N'-tetramethylperidine 鎓,), tetrahydropyrimidine quinone compound (1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6- Tetrahydropyrimidine, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,5-tetramethyl-1,4,5,6- Tetrahydropyrimidine, 8-methyl-1,8-diazabicyclo[5.4.0]-7-undecene, 5-methyl-1,5-diazabicyclo[4.3.0]- 5-decene oxime, 8-ethyl-1,8-diazabicyclo[5.4.0]-7-undecene oxime, 5-ethyl-1,5-diazabicyclo[4.3.0] -5-nonene, etc.), pyridinium compound (N-methylpyridinium, etc.), imidazolinium compound (1,2,3-trimethylimidazolinium, 1-methyl-2,3, 4-triethylimidazolinium, 1,1,2,4,5-pentamethylimidazolinium, etc., imidazolium-based compound (1,3-dimethylimidazolium, 1-ethyl-3- Methylimidazolium, 1,2,3,4-tetramethylimidazolium, 1,3,4-trimethyl-2-ethylimidazolium, 1,3-dimethyl-2,4-diethyl Imidazolium, 1,1-dimethyl-2-(4'-heptyl)imidazolium, 1,1-dimethyl-2-dodecylimidazolium, 1,1-dimethylimidazolium , 1,1,2,5-tetramethylimidazolium, 1,1,2,4,5-pentamethylimidazolium, etc.), quinolinium-based compounds (N-methylquinolinium, etc.), Pyridinium A compound (N-methyl-2,2'-bipyridinium, etc.).

該等四級銨基之中，就複合材料之強度之觀點而言，較佳為四烷基銨系化合物、哌鎓系化合物及四氫嘧啶鎓系化合物，進而較佳為四氫嘧啶鎓系化合物。 Among the quaternary ammonium groups, from the viewpoint of the strength of the composite material, a tetraalkylammonium compound or a piperidine is preferred. The oxime compound and the tetrahydropyrimidine compound are more preferably a tetrahydropyrimidine compound.

作為四級銨鹽之陰離子，可列舉：鹵素離子(氟化物陰離子、氯化物陰離子、溴化物陰離子及碘化物陰離子)、氫氧化物陰離子、羧酸根陰離子(甲酸根離子、乙酸根離子、丙酸根離子、草酸根離子、順丁烯二酸根離子、苯甲酸根離子等)、硫酸根陰離子、硝酸根陰離子、亞硝酸根陰離子、苯磺酸根陰離子、及甲苯磺酸根陰離子、含磷原子之陰離子(磷酸根離子、亞磷酸根離子、次亞磷酸根離子等)、碳酸根離子、含氮原子之雜環陰離子(苯并***、鄰苯二甲醯亞胺等)。 Examples of the anion of the quaternary ammonium salt include a halogen ion (fluoride anion, chloride anion, bromide anion, and iodide anion), a hydroxide anion, and a carboxylate anion (formate ion, acetate ion, propionate) Ions, oxalate ions, maleate ions, benzoate ions, etc.), sulfate anions, nitrate anions, nitrite anions, benzenesulfonate anions, and tosylate anions, anions containing phosphorus atoms ( a phosphate ion, a phosphite ion, a hypophosphite ion, etc.), a carbonate ion, a heterocyclic anion containing a nitrogen atom (benzotriazole, phthalimide, etc.).

該等陰離子之中，就複合材料之強度之觀點而言，較佳為鹵素離子。 Among these anions, a halogen ion is preferred from the viewpoint of the strength of the composite.

四級銨鹽之中，就複合材料之強度之觀點而言，較佳為四烷基銨鹵化物、哌鎓鹵化物及四氫嘧啶鎓鹵化物，進而較佳為5-甲基-1,5-二氮雜雙環[4.3.0]-5-壬烯鎓鹵化物及8-乙基-1,8-二氮雜雙環[5.4.0]-7-十一烯鎓鹵化物。 Among the quaternary ammonium salts, from the viewpoint of the strength of the composite material, a tetraalkylammonium halide or a piper is preferred. a ruthenium halide and a tetrahydropyrimidinium halide, further preferably 5-methyl-1,5-diazabicyclo[4.3.0]-5-nonene oxime halide and 8-ethyl-1,8 -Diazabicyclo[5.4.0]-7-undecene quinone halide.

四級鏻鹽係由四級鏻基與陰離子所構成，可藉由日本特開平2-40389號公報、日本特開平3-74395號公報、日本特開2002-97182號 公報、技報堂社「現代有機合成系列5有機磷化合物」等中所公開之公知之技術而進行合成。 The quaternary phosphonium salt is composed of a quaternary sulfhydryl group and an anion, and is disclosed in Japanese Laid-Open Patent Publication No. Hei 2-40389, Japanese Patent Application Laid-Open No. Hei No. 3-74395, and No. 2002-97182 The synthesis is carried out in a publicly known technique disclosed in the "Modern Organic Synthesis Series 5 Organic Phosphorus Compound" of the Gazette.

作為四級鏻基，可列舉以下之脂肪族鏻基及芳香族鏻基。 Examples of the quaternary fluorenyl group include the following aliphatic fluorenyl groups and aromatic fluorenyl groups.

作為脂肪族鏻基，可列舉：四甲基鏻、乙基三甲基鏻、三乙基甲基鏻、四乙基鏻、二乙基二甲基鏻、三甲基正丙基鏻、三甲基異丙基鏻、二第三丁基二甲基鏻、正丁基異丁基二甲基鏻、四丁基鏻、三甲基十八烷基鏻、三正辛基甲基鏻、(2-乙醯氧基乙基)三甲基鏻、(2-甲氧基乙氧基甲基)三乙基鏻、(2-甲氧基乙氧基甲基)三乙基鏻、乙基三正辛基鏻等。作為芳香族鏻基，可列舉：四苯基鏻、三苯基甲基鏻、二苯基二甲基鏻、乙基三苯基鏻、正丁基三苯基鏻、苄基三苯基鏻、異丙基三苯基鏻、乙烯基三苯基鏻、烯丙基三苯基鏻、三苯基丙炔基鏻、第三丁基三苯基鏻、苄基三甲基鏻等。四級鏻基亦可為上述2種以上之混合物。 Examples of the aliphatic fluorenyl group include tetramethyl hydrazine, ethyl trimethyl hydrazine, triethyl methyl hydrazine, tetraethyl hydrazine, diethyl dimethyl hydrazine, trimethyl n-propyl fluorene, and three. Methyl isopropyl hydrazine, di-tert-butyl dimethyl hydrazine, n-butyl isobutyl dimethyl hydrazine, tetrabutyl hydrazine, trimethyl octadecyl hydrazine, tri-n-octylmethyl hydrazine, (2-Ethyloxyethyl)trimethylhydrazine, (2-methoxyethoxymethyl)triethylhydrazine, (2-methoxyethoxymethyl)triethylhydrazine, B Base three Zheng Xinji and so on. Examples of the aromatic fluorenyl group include tetraphenylphosphonium, triphenylmethylhydrazine, diphenyldimethylhydrazine, ethyltriphenylphosphonium, n-butyltriphenylphosphonium, and benzyltriphenylphosphonium. And isopropyltriphenylphosphonium, vinyltriphenylphosphonium, allyltriphenylphosphonium, triphenylpropynylphosphonium, tert-butyltriphenylphosphonium, benzyltrimethylphosphonium, and the like. The quaternary fluorenyl group may also be a mixture of two or more of the above.

作為四級鏻鹽之陰離子，可列舉與上述四級銨鹽之陰離子相同者。該等陰離子之中，較佳為鹵素離子。 The anion of the quaternary phosphonium salt may be the same as the anion of the above quaternary ammonium salt. Among these anions, a halogen ion is preferred.

作為四級鏻鹽，例如可列舉：溴化四甲基鏻、溴化四丁基鏻、溴化三甲基十八烷基鏻、氫氧化三甲基十八烷基鏻、三甲基十八烷基鏻乙酸酯、三甲基十八烷基鏻-對甲苯磺酸鹽、三甲基十八烷基鏻鹽酸鹽、三甲基十八烷基鏻四氯碘酸鹽、三甲基十八烷基鏻硫酸氫鹽、三甲基十八烷基鏻甲基硫酸鹽、氫氧化苄基三甲基鏻、苄基三甲基鏻乙酸酯、苄基三甲基鏻苯甲酸鹽、苄基三甲基鏻-對甲苯磺酸鹽、溴化四苯基鏻、氫氧化四苯基鏻、氯化(2-甲氧基乙氧基甲基)三乙基鏻、氯化(2-乙醯氧基乙基)三甲基鏻等。 As the quaternary phosphonium salt, for example, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, trimethyloctadecylphosphonium bromide, trimethyloctadecylphosphonium hydroxide, trimethyl 10 Octaalkyl hydrazine acetate, trimethyl octadecyl hydrazine-p-toluene sulfonate, trimethyl octadecyl hydrazine hydrochloride, trimethyl octadecyl hydrazine tetrachloroiodide, three Methyl octadecyl sulfonium hydrogen sulfate, trimethyl octadecyl hydrazine methyl sulfate, benzyl trimethyl hydrazine hydroxide, benzyl trimethyl hydrazine acetate, benzyl trimethyl fluorene benzene Formate, benzyltrimethylphosphonium-p-toluenesulfonate, tetraphenylphosphonium bromide, tetraphenylphosphonium hydroxide, (2-methoxyethoxymethyl)triethylphosphonium chloride, Chloro(2-ethoxymethoxyethyl)trimethylhydrazine or the like.

該等之中，就複合材料之強度之觀點而言，較佳為溴化四丁基鏻及溴化四苯基鏻。 Among these, from the viewpoint of the strength of the composite material, tetrabutylphosphonium bromide and tetraphenylphosphonium bromide are preferred.

作為膦化合物，例如可列舉：三乙基膦、三丙基膦、三丁基膦、三第三丁基膦、三戊基膦、三己基膦、三環戊基膦、三環己基膦、三辛基膦、三苯基膦、三(2-呋喃基)膦、二甲基丙基膦、二甲基丁基膦、二甲基戊基膦、二甲基環己基膦、二甲基辛基膦、二甲基十八烷基膦、二甲基二十二烷基膦、二乙基丙基膦、二-十四烷基甲基膦、二-十四烷基乙基膦、二-十四烷基丙基膦、二丁基丙醇膦、二異丁基丙醇膦、二第三丁基丙醇膦、二(2-乙基己基)丙醇膦、甲基二甲醇膦、乙基二甲醇膦異丙基二甲醇膦、丁基二甲醇膦、三間甲苯基膦、及三-2,6-二甲氧基苯基膦等。 Examples of the phosphine compound include triethylphosphine, tripropylphosphine, tributylphosphine, tri-tert-butylphosphine, tripentylphosphine, trihexylphosphine, tricyclopentylphosphine, and tricyclohexylphosphine. Trioctylphosphine, triphenylphosphine, tris(2-furyl)phosphine, dimethylpropylphosphine, dimethylbutylphosphine, dimethylpentylphosphine, dimethylcyclohexylphosphine, dimethyl Octylphosphine, dimethyloctadecylphosphine, dimethyl behenylphosphine, diethylpropylphosphine, di-tetradecylmethylphosphine, di-tetradecylethylphosphine, Di-tetradecylpropylphosphine, dibutylpropanol phosphine, diisobutylpropanol phosphine, di-t-butylpropanol phosphine, bis(2-ethylhexyl)propanol phosphine, methyl dimethanol Phosphine, ethyl dimethanol phosphine isopropyl dimethanol phosphine, butyl dimethanol phosphine, tri-tolyl phosphine, and tris-2,6-dimethoxyphenyl phosphine.

該等之中，就複合材料之強度之觀點而言，較佳為三丁基膦及三苯基膦。 Among these, from the viewpoint of the strength of the composite material, preferred are tributylphosphine and triphenylphosphine.

反應性化合物(B)之中，就複合材料之強度之觀點而言，較佳為封端異氰酸酯。 Among the reactive compounds (B), from the viewpoint of the strength of the composite material, a blocked isocyanate is preferred.

聚酯樹脂(A)與反應性化合物(B)之重量比[(A)/(B)]為99.9/0.1~10/90，就同時實現纖維束之集束性與複合材料之強度之觀點而言，較佳為99.5/0.5~20/80，尤佳為99/1~50/50。 The weight ratio [(A)/(B)] of the polyester resin (A) to the reactive compound (B) is 99.9/0.1 to 10/90, and at the same time, the bundle property of the fiber bundle and the strength of the composite material are achieved. In other words, it is preferably 99.5/0.5~20/80, especially preferably 99/1~50/50.

就纖維束之集束性之觀點而言，聚酯樹脂(A)之含量基於纖維用集束劑組成物之合計重量，較佳為10~99.9重量%，進而較佳為20~90重量%，尤佳為30~80重量%。同樣地，反應性化合物(B)之含量基於纖維用集束劑組成物之合計重量，較佳為0.1~20重量%，進而較佳為0.2~10重量%，尤佳為0.5~5重量%。 The content of the polyester resin (A) is preferably from 10 to 99.9% by weight, and more preferably from 20 to 90% by weight, based on the total weight of the fiber sizing agent composition, from the viewpoint of the bundle property of the fiber bundle. Good is 30~80% by weight. Similarly, the content of the reactive compound (B) is preferably from 0.1 to 20% by weight, more preferably from 0.2 to 10% by weight, even more preferably from 0.5 to 5% by weight, based on the total weight of the fiber sizing agent composition.

本發明之纖維用集束劑組成物除含有聚酯樹脂(A)及反應性化合物(B)以外，亦可含有聚酯樹脂(A)以外之樹脂(C)、界面活性劑(D)及其他添加劑(E)之至少一種。 The fiber sizing agent composition of the present invention may contain a resin (C) other than the polyester resin (A), a surfactant (D), and the like in addition to the polyester resin (A) and the reactive compound (B). At least one of the additives (E).

若本發明之纖維用集束劑組成物含有樹脂(C)，則基質樹脂對纖維束之含浸性變得良好，故而複合材料之強度優異。又，若本發明之纖維用集束劑組成物含有界面活性劑(D)，則附著於無機纖維之集束劑容易變得平滑，故而無機纖維束之耐摩擦性更優異，易於製作不含大量有機溶劑之水性乳液。 When the fiber sizing agent composition of the present invention contains the resin (C), the matrix resin has good impregnation with the fiber bundle, and therefore the strength of the composite material is excellent. Further, when the fiber sizing agent composition of the present invention contains the surfactant (D), the sizing agent adhering to the inorganic fibers is likely to be smooth, so that the inorganic fiber bundle is more excellent in abrasion resistance, and it is easy to produce a large amount of organic An aqueous emulsion of a solvent.

作為聚酯樹脂(A)以外之樹脂(C)，可列舉：聚乙烯樹脂、聚丙烯樹脂、聚苯乙烯樹脂、聚胺酯樹脂(polyurethane resin)、聚醯胺樹脂、(甲基)丙烯酸酯樹脂及聚酯樹脂(A)以外之聚酯樹脂等熱塑性樹脂、以及環氧樹脂、(甲基)丙烯酸酯改質樹脂及不飽和聚酯樹脂等熱硬化性樹脂。亦可併用該等之2種以上。再者，所謂(甲基)丙烯酸酯係指丙烯酸酯及甲基丙烯酸酯。又，聚酯樹脂(A)及(A)以外之聚酯樹脂中不含不飽和聚酯樹脂。 Examples of the resin (C) other than the polyester resin (A) include a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyurethane resin, a polyamide resin, and a (meth) acrylate resin. A thermoplastic resin such as a polyester resin other than the polyester resin (A), and a thermosetting resin such as an epoxy resin, a (meth) acrylate modified resin, and an unsaturated polyester resin. Two or more of these may be used in combination. In addition, the (meth)acrylate means an acrylate and a methacrylate. Further, the polyester resin other than the polyester resins (A) and (A) does not contain an unsaturated polyester resin.

作為聚胺酯樹脂，可列舉由高分子多元醇、有機二異氰酸酯、及視需要之鏈伸長劑及/或交聯劑衍生而成者。 Examples of the polyurethane resin include those derived from a polymer polyol, an organic diisocyanate, and, if necessary, a chain extender and/or a crosslinking agent.

作為上述高分子多元醇，可列舉：聚酯多元醇(例如聚己二酸伸乙酯二醇(polyethylene adipate diol)、聚己二酸伸丁酯二醇、聚己二酸伸乙基伸丁酯二醇、聚己二酸新戊酯二醇、聚對苯二甲酸新戊酯二醇、聚己內酯二醇、聚戊內酯二醇及聚六亞甲基碳酸酯二醇等)；聚醚多元醇(例如聚乙二醇、聚丙二醇、聚伸乙基丙二醇、聚四亞甲基二醇、及雙酚類之 碳數2~4之AO加成物等)等。 Examples of the polymer polyol include a polyester polyol (for example, polyethylene adipate diol, polybutylene adipate butyl diol, poly(adipic acid) butyl butyl acrylate. a diol, a polypentamethylene adipate diol, a poly(p-butylene terephthalate diol, a polycaprolactone diol, a polyvalerolactone diol, and a polyhexamethylene carbonate diol, etc.); Polyether polyols (eg, polyethylene glycol, polypropylene glycol, polyethylidene glycol, polytetramethylene glycol, and bisphenols) AO adducts with a carbon number of 2 to 4, etc.).

作為上述有機二異氰酸酯之具體例，例如可列舉：2,4'-或4,4'-二苯基甲烷二異氰酸酯(MDI)、2,4-或2,6-甲苯二異氰酸酯(TDI)、4,4'-二苄基二異氰酸酯、1,3-或1,4-苯二異氰酸酯、1,5-萘二異氰酸酯、苯二甲基二異氰酸酯等芳香族二異氰酸酯；伸乙基二異氰酸酯、六亞甲基二異氰酸酯(HDI)、離胺酸二異氰酸酯等脂肪族二異氰酸酯；異佛爾酮二異氰酸酯(IPDI)、4,4'-二環己基甲烷二異氰酸酯等脂環式二異氰酸酯；及該等之2種以上之混合物。 Specific examples of the organic diisocyanate include 2,4'- or 4,4'-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-toluene diisocyanate (TDI), An aromatic diisocyanate such as 4,4'-dibenzyl diisocyanate, 1,3- or 1,4-phenylene diisocyanate, 1,5-naphthalene diisocyanate or benzene dimethyl diisocyanate; An aliphatic diisocyanate such as hexamethylene diisocyanate (HDI) or a diisocyanate diisocyanate; an alicyclic diisocyanate such as isophorone diisocyanate (IPDI) or 4,4'-dicyclohexylmethane diisocyanate; A mixture of two or more of these.

環氧樹脂為分子中具有至少1個縮水甘油基之樹脂，可列舉：單環氧化物、二環氧化物、苯酚酚醛清漆型環氧樹脂及環氧化不飽和脂肪酸三酸甘油酯(環氧化大豆油及環氧化菜籽油等)等。 The epoxy resin is a resin having at least one glycidyl group in the molecule, and examples thereof include a monoepoxide, a diepoxide, a phenol novolac type epoxy resin, and an epoxidized unsaturated fatty acid triglyceride (large epoxidation) Soybean oil and epoxidized rapeseed oil, etc.).

作為單環氧化物，可列舉如下者等：為碳數1~30之一元醇與表氯醇之縮合物(包含聚縮物)，且末端為縮水甘油醚。作為碳數1~30之一元醇，可列舉：甲醇、乙醇、丁醇、己醇、環己醇、辛醇、十二烷基醇、十四烷基醇、硬脂醇、二十烷基醇、山萮醇、二十四烷基醇及三十烷基醇等。 The monoepoxide may, for example, be a condensate of a monohydric alcohol having 1 to 30 carbon atoms and epichlorohydrin (including a polycondensate), and the terminal is a glycidyl ether. Examples of the monohydric alcohol having 1 to 30 carbon atoms include methanol, ethanol, butanol, hexanol, cyclohexanol, octanol, dodecyl alcohol, tetradecyl alcohol, stearyl alcohol, and eicosyl alcohol. Alcohol, behenyl alcohol, tetracosyl alcohol, and triacontanol.

作為二環氧化物，可列舉：二縮水甘油醚、二縮水甘油酯、二縮水甘油基胺及脂環式二環氧化物等。 Examples of the diepoxide include diglycidyl ether, diglycidyl ester, diglycidylamine, and alicyclic diepoxide.

作為二縮水甘油醚，可列舉二元酚之二縮水甘油醚及二元醇之二縮水甘油醚。 Examples of the diglycidyl ether include diglycidyl ether of a dihydric phenol and diglycidyl ether of a diol.

作為二元酚之二縮水甘油醚，可列舉如下者等：為碳數6~30之二元酚與表氯醇之縮合物(包含聚縮物)，且兩末端為縮水甘油醚。作為二元酚， 可列舉：雙酚(雙酚F、雙酚A、雙酚B、雙酚AD、雙酚S及鹵化雙酚A等)、兒茶素、間苯二酚、對苯二酚、1,5-二羥基萘、二羥基聯苯、八氯-4,4'-二羥基聯苯、四甲基聯苯及9,9'-雙(4-羥苯基)茀等。 Examples of the diglycidyl ether of the dihydric phenol include a condensate (including a polycondensate) of a dihydric phenol having a carbon number of 6 to 30 and epichlorohydrin, and both ends are glycidyl ether. As a dihydric phenol, Examples thereof include bisphenol (bisphenol F, bisphenol A, bisphenol B, bisphenol AD, bisphenol S, and halogenated bisphenol A), catechin, resorcin, hydroquinone, 1,5 - Dihydroxynaphthalene, dihydroxybiphenyl, octachloro-4,4'-dihydroxybiphenyl, tetramethylbiphenyl, and 9,9'-bis(4-hydroxyphenyl)anthracene.

作為二元醇之二縮水甘油醚，可列舉如下者等：為碳數2~200之二元醇與表氯醇之縮合物(包含聚縮物)，且兩末端為縮水甘油醚。作為二元醇，可列舉：乙二醇、丙二醇、四亞甲基二醇、1,6-己二醇、聚乙二醇、聚丙二醇、聚四亞甲醚二醇及新戊二醇等脂肪族二醇、該等脂肪族二醇與二元酚之AO加成物(碳數2~4)及末端具有2個羥基之上述聚胺酯樹脂等。 Examples of the diglycidyl ether of the diol include a condensate (including a polycondensate) of a diol having 2 to 200 carbon atoms and epichlorohydrin, and both ends are glycidyl ether. Examples of the glycol include ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and neopentyl glycol. An aliphatic diol, an AO adduct of these aliphatic diols and a dihydric phenol (carbon number 2 to 4), and the above-mentioned polyurethane resin having two hydroxyl groups at the terminal.

二縮水甘油醚中所含之二元酚單元或二元醇單元與表氯醇單元之莫耳比{(二元酚單元或二元醇單元)：(表氯醇單元)}係由n：n+1所表示。n較佳為1~10，進而較佳為1~8，尤佳為1~5。二縮水甘油醚亦可為n=1~10之混合物(縮聚度不同之混合物等)。 The molar ratio of the dihydric phenol unit or the diol unit contained in the diglycidyl ether to the epichlorohydrin unit {(divalent phenol unit or diol unit): (epichlorohydrin unit)} is composed of n: Expressed by n+1. n is preferably from 1 to 10, more preferably from 1 to 8, and particularly preferably from 1 to 5. The diglycidyl ether may also be a mixture of n = 1 to 10 (mixtures having different degrees of polycondensation, etc.).

作為二縮水甘油酯，可列舉芳香族二羧酸之二縮水甘油酯及脂肪族二羧酸之二縮水甘油酯等。 Examples of the diglycidyl ester include diglycidyl ester of an aromatic dicarboxylic acid and diglycidyl ester of an aliphatic dicarboxylic acid.

作為芳香族二羧酸之二縮水甘油酯，可列舉如下者等：為芳香族二羧酸與表氯醇之縮合物(包含聚縮物)，且具有2個縮水甘油基。 Examples of the diglycidyl ester of the aromatic dicarboxylic acid include a condensate of an aromatic dicarboxylic acid and epichlorohydrin (including a polycondensate) and two glycidyl groups.

作為脂肪族二羧酸之二縮水甘油酯，可列舉如下者等：為芳香族二羧酸之芳香核氫化物(六氫鄰苯二甲酸及4-環己烯-1,2-二羧酸等)或直鏈或支鏈之脂肪族二羧酸(己二酸及2,2-二甲基丙烷二羧酸等)與表氯醇之縮合物(包含聚縮物)，且具有2個縮水甘油基。 Examples of the diglycidyl ester of the aliphatic dicarboxylic acid include aromatic hydrides of aromatic dicarboxylic acids (hexahydrophthalic acid and 4-cyclohexene-1,2-dicarboxylic acid). Or a linear or branched aliphatic dicarboxylic acid (adipate and 2,2-dimethylpropane dicarboxylic acid, etc.) and epichlorohydrin condensate (including polycondensate), and has 2 Glycidyl group.

二縮水甘油酯中所含之芳香族二羧酸單元或脂肪族二羧酸單元與表氯醇單元之莫耳比{(芳香族二羧酸單元或脂肪族二羧酸單元)： (表氯醇單元)}係由n：n+1所表示。n較佳為1~10，進而較佳為1~8，尤佳為1~5。二縮水甘油酯亦可為n=1~10之混合物。 The molar ratio of the aromatic dicarboxylic acid unit or the aliphatic dicarboxylic acid unit and the epichlorohydrin unit contained in the diglycidyl ester {(aromatic dicarboxylic acid unit or aliphatic dicarboxylic acid unit): (epichlorohydrin unit)} is represented by n:n+1. n is preferably from 1 to 10, more preferably from 1 to 8, and particularly preferably from 1 to 5. The diglycidyl ester may also be a mixture of n = 1 to 10.

作為二縮水甘油基胺，可列舉藉由碳數6~20、且具有2~4個活性氫原子之芳香族胺(苯胺及甲苯胺等)與表氯醇之反應而獲得之N-縮水甘油基化物(N,N-二縮水甘油基苯胺及N,N-二縮水甘油基甲苯胺等)等。 Examples of the diglycidylamine include N-glycidol obtained by reacting an aromatic amine (aniline, toluidine, etc.) having 2 to 4 active hydrogen atoms with epichlorohydrin. A compound (N,N-diglycidylaniline, N,N-diglycidyltoluidine, etc.) or the like.

二縮水甘油基胺中所含之芳香族胺單元與表氯醇單元之莫耳比{(芳香族胺單元)：(表氯醇單元)}係由n：n+1所表示。n較佳為1~10，進而較佳為1~8，尤佳為1~5。二縮水甘油基胺亦可為n=1~10之混合物。 The molar ratio {(aromatic amine unit): (epichlorohydrin unit)) of the aromatic amine unit and the epichlorohydrin unit contained in the diglycidylamine is represented by n:n+1. n is preferably from 1 to 10, more preferably from 1 to 8, and particularly preferably from 1 to 5. The diglycidylamine may also be a mixture of n = 1 to 10.

作為脂環式二環氧化物，可列舉碳數6~50、且環氧基之數量為2個之脂環式環氧化物{二氧化乙烯基環己烯、二氧化檸檬烯、二氧化二環戊二烯、雙(2,3-環氧環戊基)醚、乙二醇二環氧二環戊醚、雙(3,4-環氧-6-甲基環己基甲基)己二酸酯及雙(3,4-環氧-6-甲基環己基甲基)丁基胺等}。 Examples of the alicyclic diepoxide include an alicyclic epoxide having a carbon number of 6 to 50 and an epoxy group, {ethylene oxide cyclohexene oxide, limonene dioxide, and dioxane dioxide. Pentadiene, bis(2,3-epoxycyclopentyl) ether, ethylene glycol digoxy dicyclopentyl ether, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipic acid Ester and bis(3,4-epoxy-6-methylcyclohexylmethyl)butylamine, etc.}.

作為(甲基)丙烯酸酯改質樹脂，可列舉(甲基)丙烯酸酯改質熱塑性樹脂及乙烯酯樹脂。 Examples of the (meth) acrylate-modified resin include a (meth) acrylate-modified thermoplastic resin and a vinyl ester resin.

作為(甲基)丙烯酸酯改質熱塑性樹脂，包含利用(甲基)丙烯酸對具有醇性羥基之熱塑性樹脂{聚胺酯、聚酯及聚醚(聚丙二醇及聚乙二醇等)等}之羥基進行改質而成之改質物，可列舉：聚(二-/單-)(甲基)丙烯酸胺酯、聚酯(二-/單-)(甲基)丙烯酸酯及聚醚(二-/單-)(甲基)丙烯酸酯等。再者，所謂(二-/單-)(甲基)丙烯酸酯係指二(甲基)丙烯酸酯及單(甲基)丙烯 酸酯。 The (meth) acrylate-modified thermoplastic resin includes a hydroxyl group (polyurethane ester, polyester, polyether (polypropylene glycol, polyethylene glycol, etc.), etc.) having an alcoholic hydroxyl group by (meth)acrylic acid. Modified materials can be exemplified by poly(di-/mono-) (meth) acrylate, polyester (di-/mono-) (meth) acrylate and polyether (di-/single) -) (meth) acrylate or the like. Furthermore, the term "di-/mono-) (meth) acrylate means di(meth) acrylate and mono (meth) propylene. Acid ester.

作為乙烯酯樹脂，可列舉雙酚型環氧樹脂(甲基)丙烯酸酯改質物{雙酚A型環氧樹脂之環氧基與(甲基)丙烯酸之羧基進行反應而獲得之末端(甲基)丙烯酸酯改質樹脂等}等。 Examples of the vinyl ester resin include a bisphenol type epoxy resin (meth) acrylate modified product (the terminal obtained by reacting an epoxy group of a bisphenol A type epoxy resin with a carboxyl group of (meth)acrylic acid (methyl group). ) acrylate modified resin, etc.}.

作為不飽和聚酯樹脂，可列舉使含有α,β-不飽和二羧酸之酸成分與醇反應，並使所獲得之不飽和聚酯溶解於聚合性不飽和單體而成者等。作為α,β-不飽和二羧酸，可列舉：順丁烯二酸、反丁烯二酸、衣康酸等及該等之酸酐等衍生物等，該等亦可併用2種以上。又，視需要亦可將作為α,β-不飽和二羧酸以外之酸性成分的鄰苯二甲酸、間苯二甲酸、對苯二甲酸、四氫鄰苯二甲酸、己二酸、癸二酸等飽和二羧酸及該等之酸酐等衍生物與α,β-不飽和二羧酸併用。作為醇，可列舉：乙二醇、二乙二醇、丙二醇、二丙二醇、1,2-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇等脂肪族二醇；環戊二醇、環己二醇等脂環式二醇；氫化雙酚A、雙酚A之環氧丙烷(1~100莫耳)加成物、二甲苯二醇等芳香族二醇；三羥甲基丙烷、新戊四醇等多元醇等，亦可併用該等之2種以上。 The unsaturated polyester resin may be one obtained by reacting an acid component containing an α,β-unsaturated dicarboxylic acid with an alcohol, and dissolving the obtained unsaturated polyester in a polymerizable unsaturated monomer. Examples of the α,β-unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, and the like, and derivatives such as these acid anhydrides, and these may be used in combination of two or more kinds. Further, as the acidic component other than the α,β-unsaturated dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and anthracene may be used as needed. A saturated dicarboxylic acid such as an acid or a derivative such as an acid anhydride is used in combination with an α,β-unsaturated dicarboxylic acid. Examples of the alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. Aliphatic diol; alicyclic diol such as cyclopentanediol or cyclohexanediol; hydrogenated bisphenol A, bisphenol A propylene oxide (1~100 mol) adduct, xylene glycol, etc. A diol or a polyhydric alcohol such as trimethylolpropane or neopentyl alcohol may be used in combination of two or more kinds thereof.

作為具體例，例如包含反丁烯二酸或順丁烯二酸與雙酚A之環氧乙烷加成物之縮合物、反丁烯二酸或順丁烯二酸與雙酚A之環氧丙烷加成物之縮合物、及反丁烯二酸或順丁烯二酸與雙酚A之環氧乙烷環氧丙烷加成物(可為無規亦可為嵌段)之縮合物等，該等縮合物視需要亦可為溶解於苯乙烯等單體而成者。 As a specific example, for example, a condensate of fumaric acid or an ethylene oxide adduct of maleic acid and bisphenol A, a ring of fumaric acid or maleic acid and bisphenol A is contained. a condensate of an oxypropane adduct, and an condensate of fumaric acid or maleic acid and bisphenol A ethylene oxide propylene oxide adduct (which may be random or block) The condensate may be dissolved in a monomer such as styrene as needed.

作為上述聚酯樹脂(A)以外之聚酯樹脂，可列舉：使上述二羧酸(a1)及/或二羧酸之酸酐(a2)與二醇(b)反應而獲得之聚酯樹 脂、內酯開環聚合物及聚羥基羧酸等(任一者之HLB均不為4~18、或於30℃之黏度不為10~1,000,000Pa‧s者)。 The polyester resin other than the polyester resin (A) may be a polyester tree obtained by reacting the acid anhydride (a2) of the dicarboxylic acid (a1) and/or the dicarboxylic acid with the diol (b). Lipid, lactone ring-opening polymer and polyhydroxycarboxylic acid (either HLB is not 4 to 18, or the viscosity at 30 ° C is not 10 to 1,000,000 Pa‧s).

作為內酯開環聚合物，可列舉使用金屬氧化物及有機金屬化合物等觸媒，使碳數3~12之單內酯(環中之酯基數為1個)等內酯類(β-丙內酯、γ-丁內酯、δ-戊內酯及ε-己內酯等)進行開環聚合而獲得者等。 Examples of the lactone ring-opening polymer include lactones such as metal oxides and organometallic compounds, and lactones (β-propyl) such as a monolactone having 3 to 12 carbon atoms (one in the ring). A lactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone or the like is obtained by ring-opening polymerization.

作為聚羥基羧酸，可列舉使羥基羧酸(乙醇酸及乳酸等)進行脫水縮合而獲得者。 The polyhydroxycarboxylic acid is obtained by dehydration condensation of a hydroxycarboxylic acid (glycolic acid, lactic acid, etc.).

樹脂(C)之中，就複合材料之強度等觀點而言，較佳為環氧樹脂、聚胺酯樹脂、(甲基)丙烯酸酯樹脂、不飽和聚酯樹脂、聚醯胺樹脂及上述聚酯樹脂(A)以外之聚酯樹脂，進而較佳為環氧樹脂、聚胺酯樹脂、(甲基)丙烯酸酯樹脂及不飽和聚酯樹脂，尤佳為環氧樹脂。 Among the resins (C), from the viewpoints of the strength of the composite material, etc., epoxy resin, polyurethane resin, (meth) acrylate resin, unsaturated polyester resin, polyamide resin, and the above polyester resin are preferable. The polyester resin other than (A) is more preferably an epoxy resin, a polyurethane resin, a (meth) acrylate resin or an unsaturated polyester resin, and particularly preferably an epoxy resin.

於使用樹脂(C)之情形時，其含量基於纖維用集束劑組成物之合計重量，就基質樹脂之含浸性之觀點而言，較佳為1~90重量%，更佳為5~80重量%，進而較佳為10~75重量%，尤佳為10~50重量%。 In the case of using the resin (C), the content thereof is based on the total weight of the fiber sizing agent composition, and from the viewpoint of the impregnation property of the matrix resin, it is preferably from 1 to 90% by weight, more preferably from 5 to 80% by weight. %, further preferably 10 to 75% by weight, particularly preferably 10 to 50% by weight.

作為界面活性劑(D)，可列舉：非離子界面活性劑、陰離子界面活性劑、陽離子界面活性劑及兩性界面活性劑等界面活性劑等。該等亦可併用2種以上。 Examples of the surfactant (D) include a surfactant such as a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. These may also be used in combination of 2 or more types.

作為非離子界面活性劑，例如可列舉：環氧烷加成型非離子界面活性劑[例如高級醇(碳數8~18)或高級脂肪酸(碳數12~24)之AO加成物；烷基苯酚(碳數10~20)、苯乙烯化苯酚(碳數14~62)、苯乙烯化異丙苯基苯酚或苯乙烯化甲酚(碳數15~61)之AO加成物；使聚伸烷 基二醇與高級脂肪酸反應而成者；使多元(2元~8元或其以上)醇(碳數2~32，例如乙二醇、丙二醇、甘油、新戊四醇、山梨醇酐等)與高級脂肪酸(碳數12~24，例如月桂酸、硬脂酸)反應而獲得之酯化物之AO加成物；高級脂肪醯胺之環氧烷加成物；多元(2元~8元或其以上)醇烷基(碳數8~60)醚之AO加成物等]、及多元(2元~8元或其以上)醇(碳數2~32)型非離子界面活性劑[多元醇脂肪酸(碳數8~36)酯、多元醇烷基(碳數7~32)醚、脂肪酸(碳數8~32)烷醇醯胺等]等。 Examples of the nonionic surfactant include an alkylene oxide-added nonionic surfactant (for example, an AO adduct of a higher alcohol (carbon number 8 to 18) or a higher fatty acid (carbon number 12 to 24); an alkyl group; AO adduct of phenol (carbon number 10-20), styrenated phenol (carbon number 14-62), styrenated cumylphenol or styrenated cresol (carbon number 15~61); Alkane a reaction of a diol with a higher fatty acid; a polyhydric (2 to 8 or more) alcohol (carbon number 2 to 32, such as ethylene glycol, propylene glycol, glycerin, neopentyl alcohol, sorbitol, etc.) AO adduct of esterified product obtained by reaction with higher fatty acid (carbon number 12-24, such as lauric acid, stearic acid); alkylene oxide adduct of higher fatty decylamine; diversified (2 to 8 yuan or The above) an alcohol alkyl group (carbon number 8 to 60) ether AO adduct, etc., and a plurality of (2 yuan to 8 yuan or more) alcohol (carbon number 2 to 32) type nonionic surfactant [multiple Alcohol fatty acid (carbon number 8 to 36) ester, polyhydric alcohol alkyl group (carbon number 7 to 32) ether, fatty acid (carbon number 8 to 32) alkanol decylamine, etc.

作為陰離子界面活性劑，例如可列舉：羧酸(碳數8~22之飽和或不飽和脂肪酸)或其鹽(鈉、鉀、銨及烷醇胺等鹽)、碳數8~16之脂肪族醇之羧甲基化物之鹽、碳數8~24之脂肪族醇醚羧酸(例如碳數8~24、較佳為碳數10~18之脂肪族醇之AO 1~10莫耳加成物之羧甲基化物等)、硫酸酯鹽[高級醇硫酸酯鹽(碳數8~18之脂肪酸醇之硫酸酯鹽等)]、高級烷醚硫酸酯鹽[碳數8~18之脂肪酸醇之EO(1~10莫耳)加成物之硫酸酯鹽]、硫酸化油(將天然不飽和油脂或不飽和之蠟直接硫酸化並進行中和而成者)、硫酸化脂肪酸酯(將不飽和脂肪酸之低級醇酯加以硫酸化並進行中和而成者)、硫酸化烯烴(將碳數12~18之烯烴加以硫酸化並進行中和而成者)、磺酸鹽[烷基苯磺酸鹽、烷基萘磺酸鹽、磺基琥珀酸二酯、α-烯烴(碳數12~18)磺酸鹽及Igepon T型等]、磷酸酯鹽[高級醇(碳數8~60)磷酸酯鹽、高級醇(碳數8~60)EO加成物磷酸酯鹽、烷基(碳數8~60)苯酚環氧乙烷加成物磷酸酯鹽等]、烷基苯酚(碳數10~20)之AO加成物之硫酸酯鹽(鈉鹽、鉀鹽、銨鹽及烷醇胺鹽等)、芳基烷基苯酚[苯乙烯化苯酚(碳數14~62)、苯乙烯化異丙苯基苯酚及苯乙烯化甲酚(碳數15~61) 等]之AO加成物之硫酸酯鹽等。 Examples of the anionic surfactant include a carboxylic acid (saturated or unsaturated fatty acid having 8 to 22 carbon atoms) or a salt thereof (salts such as sodium, potassium, ammonium, and an alkanolamine) and an aliphatic having 8 to 16 carbon atoms. a salt of a carboxymethylate of an alcohol, an aliphatic alcohol ether carboxylic acid having a carbon number of 8 to 24 (for example, an AO 1 to 10 molar addition of an aliphatic alcohol having a carbon number of 8 to 24, preferably a carbon number of 10 to 18) Carboxymethylate, etc.), sulfate salt [higher alcohol sulfate salt (sulfate salt of fatty acid alcohol having 8 to 18 carbon atoms, etc.)], higher alkyl ether sulfate salt [fatty acid alcohol having 8 to 18 carbon atoms Sulfate salt of EO (1~10 mol) adduct], sulfated oil (which is directly sulfated and neutralized by natural unsaturated oil or unsaturated wax), sulfated fatty acid ester ( Sulfating olefins (by sulfating and neutralizing olefins having 12 to 18 carbon atoms) by sulfating and lowering the lower alcohol ester of unsaturated fatty acid), sulfonate [alkyl Benzene sulfonate, alkylnaphthalene sulfonate, sulfosuccinate diester, α-olefin (carbon number 12-18) sulfonate and Igepon T type, etc., phosphate ester salt [higher alcohol (carbon number 8~) 60) Phosphate salt, higher alcohol (carbon number 8~60) EO plus Phosphate salt, alkyl (carbon number 8 to 60) phenol ethylene oxide adduct phosphate salt, etc.], alkyl phenol (carbon number 10 to 20) AO adduct sulfate salt (sodium salt) , potassium salt, ammonium salt and alkanolamine salt, etc., arylalkylphenol [styrene phenol (carbon number 14~62), styrenated cumyl phenol and styrenated cresol (carbon number 15 ~61) Sulfate salts of AO adducts, etc.

作為陽離子界面活性劑，例如可列舉：四級銨鹽型[氯化硬脂基三甲基銨、氯化山萮基三甲基銨、氯化二硬脂基二甲基銨、及乙基硫酸羊毛脂脂肪酸胺基丙基乙基二甲基銨等]、胺鹽型[硬脂酸二乙基胺基乙基醯胺乳酸鹽、二月桂基胺鹽酸鹽及油基胺乳酸鹽等]等。 The cationic surfactant may, for example, be a quaternary ammonium salt type [chlorinated stearyltrimethylammonium chloride, benzalkonium trimethylammonium chloride, distearyldimethylammonium chloride, and ethyl group). Sulfonic acid lanolin fatty acid aminopropylethyl dimethyl ammonium, etc.], amine salt type [stearic acid diethylaminoethyl decylamine lactate, dilaurylamine hydrochloride and oleylamine lactate, etc. ]Wait.

作為兩性界面活性劑，例如可列舉：甜菜鹼型兩性界面活性劑[椰油脂肪醯胺丙基二甲基甜菜鹼、月桂基二甲基甜菜鹼、2-烷基-N-羧甲基-N-羥乙基咪唑啉鎓甜菜鹼、月桂基羥基磺基甜菜鹼、及月桂醯基醯胺乙基羥乙基羧甲基甜菜鹼羥丙基磷酸鈉等]、胺基酸型兩性界面活性劑[β-月桂基胺基丙酸鈉等]。 As the amphoteric surfactant, for example, a betaine type amphoteric surfactant [coco fat amidoxime dimethyl betaine, lauryl dimethyl betaine, 2-alkyl-N-carboxymethyl group- N-hydroxyethyl imidazolinium betaine, lauryl hydroxysultaine, and lauryl decyl hydroxyethyl carboxymethyl betaine hydroxypropyl phosphate, etc., amphoteric acid type amphoteric interfacial activity Agent [β-sodium lauryl ammonium propionate, etc.].

界面活性劑(D)中較佳者為陰離子界面活性劑、非離子界面活性劑、以及陰離子界面活性劑及非離子界面活性劑之混合物，進而較佳者為烷基苯酚之AO加成物、芳基烷基苯酚(苯乙烯化苯酚、苯乙烯化異丙苯基苯酚或苯乙烯化甲酚)之AO加成物、烷基苯酚之AO加成物之硫酸酯鹽、芳基烷基苯酚之AO加成物之硫酸酯鹽及該等之混合物，尤佳者為芳基烷基苯酚之AO加成物、芳基烷基苯酚之AO加成物之硫酸酯鹽及該等之混合物。 Preferred among the surfactant (D) are an anionic surfactant, a nonionic surfactant, and a mixture of an anionic surfactant and a nonionic surfactant, and further preferably an AO adduct of an alkylphenol, AO adduct of arylalkylphenol (styrenated phenol, styrenated cumylphenol or styrenated cresol), sulfated salt of AO adduct of alkylphenol, arylalkylphenol Sulfate salts of AO adducts and mixtures thereof are, in particular, AO adducts of arylalkylphenols, sulfate salts of AO adducts of arylalkylphenols and mixtures thereof.

於使用界面活性劑(D)之情形時，其含量基於纖維用集束劑組成物之合計重量，就纖維束之集束性之觀點而言，較佳為0.5~20重量%，進而較佳為1~15重量%，尤佳為2~10重量%。 In the case of using the surfactant (D), the content thereof is based on the total weight of the fiber sizing agent composition, and is preferably from 0.5 to 20% by weight, and further preferably 1 from the viewpoint of the bundle property of the fiber bundle. ~15% by weight, particularly preferably 2 to 10% by weight.

作為其他添加劑(E)，例如可列舉選自平滑劑、防腐劑及抗氧化劑中之1種以上。 The other additive (E) is, for example, one or more selected from the group consisting of a smoothing agent, a preservative, and an antioxidant.

作為平滑劑，可列舉：蠟類(聚乙烯、聚丙烯、氧化聚乙烯、氧化聚丙烯、改質聚乙烯、改質聚丙烯等)、高級脂肪酸烷基(碳數1~24)酯類(硬脂酸甲酯、硬脂酸乙酯、硬脂酸丙酯、硬脂酸丁酯、硬脂酸辛酯、硬脂酸硬脂酯等)、高級脂肪酸(肉豆蔻酸、棕櫚酸、硬脂酸)等。 Examples of the smoothing agent include waxes (polyethylene, polypropylene, oxidized polyethylene, oxidized polypropylene, modified polyethylene, modified polypropylene, etc.), and higher fatty acid alkyl (carbon number 1 to 24) esters ( Methyl stearate, ethyl stearate, propyl stearate, butyl stearate, octyl stearate, stearyl stearate, etc.), higher fatty acids (myristic acid, palmitic acid, stearic acid) Acid) and so on.

作為防腐劑，可列舉：苯甲酸類、水楊酸類、山梨酸類、四級銨鹽類、咪唑類等。 Examples of the preservative include benzoic acid, salicylic acid, sorbic acid, quaternary ammonium salt, and imidazole.

作為抗氧化劑，可列舉：酚類(2,6-二-第三丁基-對甲酚等)、硫代二丙酸酯類(3,3'-硫代二丙酸二月桂酯等)、亞磷酸酯類(亞磷酸三苯酯等)。 Examples of the antioxidant include phenols (2,6-di-t-butyl-p-cresol, etc.) and thiodipropionates (3,3'-dilaucuric acid dilaurate). , phosphites (triphenyl phosphite, etc.).

於使用添加劑(E)之情形時，其含量基於纖維用集束劑組成物之合計重量，為10重量%以下，較佳為5重量%以下。 In the case of using the additive (E), the content thereof is 10% by weight or less, preferably 5% by weight or less, based on the total weight of the fiber sizing agent composition.

本發明之纖維用集束劑組成物之製造方法並無特別限制，例如可列舉如下方法等：投入順序並無特別限制地向混合容器中投入聚酯樹脂(A)及反應性化合物(B)、以及視需要之樹脂(C)、界面活性劑(D)及其他添加劑(E)，較佳為於20~90℃、進而較佳為於40~80℃進行攪拌直至變得均勻而製造。 The method for producing the fiber sizing agent composition of the present invention is not particularly limited, and examples thereof include a method in which the polyester resin (A) and the reactive compound (B) are introduced into the mixing container without particular limitation. Further, if necessary, the resin (C), the surfactant (D), and other additives (E) are preferably produced by stirring at 20 to 90 ° C, more preferably at 40 to 80 ° C until uniform.

本發明之纖維用集束劑分散體較佳為由本發明之纖維用集束劑組成物分散於溶劑中而成。 The fiber sizing agent dispersion of the present invention is preferably obtained by dispersing a fiber sizing agent composition of the present invention in a solvent.

又，本發明之纖維用集束劑溶液較佳為由本發明之纖維用集束劑溶解於溶劑中而成。 Further, the fiber sizing agent solution of the present invention is preferably obtained by dissolving the fiber sizing agent of the present invention in a solvent.

藉由使纖維用集束劑組成物溶解或分散於溶劑中，容易使纖維用集束劑組成物附著於纖維束之量變得適量。 By dissolving or dispersing the fiber sizing agent composition in a solvent, it is easy to make an appropriate amount of the fiber sizing agent composition adhered to the fiber bundle.

作為溶劑，可列舉公知之溶劑、例如親水性有機溶劑[碳數1~4之低級醇(甲醇、乙醇及異丙醇等)、碳數3~6之酮(丙酮、乙基甲基酮及甲基異丁基酮等)、碳數2~6之二醇(乙二醇、丙二醇、二乙二醇及三乙二醇等)及其單烷基(碳數1~2)醚、二甲基甲醯胺以及碳數3~5之乙酸烷基酯(乙酸甲酯及乙酸乙酯等)等]等有機溶劑及水。該等亦可併用2種以上。上述溶劑之中，就安全性等觀點而言，較佳者為親水性有機溶劑與水之混合溶劑及水，進而較佳者為水。 The solvent may, for example, be a known solvent, for example, a hydrophilic organic solvent (a lower alcohol having 1 to 4 carbon atoms (such as methanol, ethanol, or isopropanol) or a ketone having 3 to 6 carbon atoms (acetone or ethyl methyl ketone). Methyl isobutyl ketone, etc., diols having 2 to 6 carbon atoms (ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, etc.) and their monoalkyl (carbon number 1 to 2) ethers, An organic solvent such as methylformamide or an alkyl acetate having 3 to 5 carbon atoms (such as methyl acetate or ethyl acetate) and water. These may also be used in combination of 2 or more types. Among the above solvents, from the viewpoint of safety and the like, a mixed solvent of a hydrophilic organic solvent and water and water are preferred, and water is more preferred.

就成本等觀點而言，本發明之纖維用集束劑分散體及纖維用集束劑溶液較佳為流通時為高濃度，且纖維束之製造時為低濃度。即，藉由以高濃度流通，可降低運輸成本及保管成本等，藉由以低濃度對纖維進行處理，可製造同時實現優異之集束性與開纖性之纖維束。 The fiber sizing agent dispersion and the fiber sizing agent solution of the present invention preferably have a high concentration at the time of circulation and a low concentration at the time of production of the fiber bundle. In other words, by circulating at a high concentration, transportation costs, storage costs, and the like can be reduced, and by processing the fibers at a low concentration, it is possible to manufacture a fiber bundle that achieves both excellent bundling properties and fiber opening properties.

關於纖維用集束劑分散體及纖維用集束劑溶液為高濃度之情形時之濃度(溶劑以外之成分之含有比率)，就保存穩定性等觀點而言，較佳為30~80重量%，進而較佳為40~70重量%。 The concentration in the case where the fiber sizing agent dispersion and the fiber sizing agent solution are in a high concentration (the content ratio of the components other than the solvent) is preferably 30 to 80% by weight in terms of storage stability and the like, and further It is preferably 40 to 70% by weight.

關於纖維用集束劑分散體及纖維用集束劑溶液為低濃度之情形時之濃度，就於纖維束之製造時可使纖維用集束劑之附著量變得適量之觀點等而言，較佳為0.5~15重量%，進而較佳為1~10重量%。 The concentration in the case where the fiber sizing agent dispersion and the fiber sizing agent solution are in a low concentration is preferably 0.5 in terms of the amount of the fiber sizing agent adhered to the fiber bundle during the production of the fiber bundle. ~15% by weight, further preferably 1 to 10% by weight.

本發明之纖維用集束劑分散體及纖維用集束劑溶液之製造方法並無特別限制，例如可列舉向“藉由上述方法所獲得之本發明之纖維用集束劑組成物”中投入溶劑，使纖維用集束劑組成物溶解或乳化分散於溶劑中之方法。 The method for producing the fiber sizing agent dispersion and the fiber sizing agent solution of the present invention is not particularly limited, and for example, a solvent is introduced into the "fiber sizing agent composition of the present invention obtained by the above method". A method in which a fiber is dissolved or emulsified in a solvent by a sizing agent composition.

關於使纖維用集束劑組成物溶解或乳化分散於溶劑中時之溫度，就容 易混合性之觀點而言，較佳為20~90℃，進而較佳為40~90℃。 Regarding the temperature at which the fiber is dissolved or emulsified in a solvent by the sizing agent composition, From the viewpoint of ease of mixing, it is preferably from 20 to 90 ° C, more preferably from 40 to 90 ° C.

使纖維用集束劑組成物溶解或乳化分散於溶劑中之時間較佳為1~20小時，進而較佳為2~10小時。 The time for dissolving or emulsifying the fiber in the solvent with the sizing agent composition is preferably from 1 to 20 hours, more preferably from 2 to 10 hours.

於使纖維用集束劑組成物溶解或乳化分散於水性媒體中時，可使用公知之混合裝置、溶解裝置及乳化分散裝置，具體而言，可使用攪拌葉片(葉片形狀：槳型及三片槳等)、圓錐型螺旋攪拌機[Hosokawa Micron股份有限公司製造等]、帶式攪拌機、錐形攪拌器、泥漿混合機、萬能混合機{萬能混合攪拌機「5DM-L」[三英製作所股份有限公司製造]等}及亨舍爾混合機[日本COKE & ENGINEERING股份有限公司等]、高壓釜等。 When the fiber sizing agent composition is dissolved or emulsified and dispersed in an aqueous medium, a known mixing device, a dissolving device, and an emulsification dispersing device can be used. Specifically, a stirring blade can be used (blade shape: paddle type and three-piece paddle) Etc.) Conical spiral mixer [manufactured by Hosokawa Micron Co., Ltd.], belt mixer, conical mixer, mud mixer, universal mixer {universal mixing mixer "5DM-L" [manufactured by Sanying Co., Ltd. ] etc.} and Henschel mixer [Japan COKE & ENGINEERING Co., Ltd., etc.], autoclave, etc.

作為可應用本發明之纖維用集束劑組成物、纖維用集束劑分散體或纖維用集束劑溶液之纖維，可列舉：玻璃纖維、碳纖維、陶瓷纖維、金屬纖維、礦物纖維及礦渣纖維等無機纖維(國際公開第2003/47830號中所記載者等)、芳綸纖維等有機纖維，就成形體強度之觀點而言，較佳為碳纖維。該等纖維亦可併用2種以上。 Examples of the fibers of the fiber sizing agent composition, the fiber sizing agent dispersion or the fiber sizing agent solution to which the present invention can be applied include inorganic fibers such as glass fibers, carbon fibers, ceramic fibers, metal fibers, mineral fibers, and slag fibers. Organic fibers such as those described in (International Publication No. 2003/47830) and aramid fibers are preferably carbon fibers from the viewpoint of the strength of the molded body. These fibers may be used in combination of two or more kinds.

於本發明之纖維束之製造方法中，可利用上述纖維用集束劑組成物、纖維用集束劑分散體或纖維用集束劑溶液，對選自由碳纖維、玻璃纖維、聚芳醯胺纖維、陶瓷纖維、金屬纖維、礦物纖維及礦渣纖維所組成之群中之至少1種纖維進行處理而獲得纖維束。所獲得之纖維束較佳為束有3,000~30,000根左右之纖維。 In the method for producing a fiber bundle of the present invention, the fiber sizing agent composition, the fiber sizing agent dispersion or the fiber sizing agent solution may be used, which is selected from the group consisting of carbon fibers, glass fibers, polyarsenamide fibers, and ceramic fibers. At least one of the group consisting of metal fibers, mineral fibers, and slag fibers is treated to obtain a fiber bundle. The fiber bundle obtained is preferably a bundle of about 3,000 to 30,000 fibers.

作為纖維之處理方法，可列舉噴霧法或浸漬法等。關於纖維用集束劑組成物於纖維上之附著量，基於纖維之重量，較佳為0.05~5重量%，進而較佳為0.2~2.5重量%。若纖維用集束劑組成物之附著量為該範圍， 則集束性優異。 Examples of the method for treating the fiber include a spray method, a dipping method, and the like. The amount of the fiber sizing agent composition adhered to the fiber is preferably 0.05 to 5% by weight, and more preferably 0.2 to 2.5% by weight, based on the weight of the fiber. If the adhesion amount of the fiber sizing agent composition is within the range, Therefore, the bundling property is excellent.

本發明之複合中間體係由如上所述般利用本發明之纖維用集束劑組成物、纖維用集束劑分散體或纖維用集束劑溶液進行過處理之纖維束與基質樹脂所構成。本發明之複合中間體視需要亦可含有觸媒。若本發明之複合中間體含有觸媒，則複合材料之拉伸強度優異。 The composite intermediate system of the present invention comprises the fiber bundle and the matrix resin which have been treated with the fiber sizing agent composition, the fiber sizing agent dispersion or the fiber sizing agent solution of the present invention as described above. The composite intermediate of the present invention may also contain a catalyst if necessary. When the composite intermediate of the present invention contains a catalyst, the composite material has excellent tensile strength.

作為基質樹脂，可列舉：聚丙烯、聚醯胺、聚對苯二甲酸乙二酯、聚碳酸酯、聚苯硫醚等熱塑性樹脂及環氧樹脂、不飽和聚酯樹脂、乙烯酯樹脂及酚系樹脂等熱硬化性樹脂。 Examples of the matrix resin include thermoplastic resins such as polypropylene, polyamide, polyethylene terephthalate, polycarbonate, and polyphenylene sulfide, and epoxy resins, unsaturated polyester resins, vinyl ester resins, and phenols. A thermosetting resin such as a resin.

作為環氧樹脂用之觸媒，可列舉公知(日本特開2005-213337號公報中所記載者等)之環氧樹脂用硬化劑及硬化促進劑等。又，作為不飽和聚酯樹脂及乙烯酯樹脂用之觸媒，可列舉：過氧化物(過氧化苯甲醯、過氧苯甲酸第三丁酯、過氧化第三丁基異丙苯等、甲基乙基酮過氧化物、1,1-二(過氧化第三丁基)丁烷、過氧化二碳酸二(4-第三丁基環己基)酯等)及偶氮系化合物(偶氮雙異戊腈等)。 As a catalyst for the epoxy resin, a curing agent for an epoxy resin, a curing accelerator, and the like which are known (such as those described in JP-A-2005-213337) can be used. Further, examples of the catalyst for the unsaturated polyester resin and the vinyl ester resin include a peroxide (benzyl peroxide, a third butyl peroxybenzoate, a third butyl cumene peroxide, etc.). Methyl ethyl ketone peroxide, 1,1-di(t-butylperoxide) butane, di(4-tert-butylcyclohexyl)peroxydicarbonate, etc., and azo compounds (even Nitrogen bisisoprene, etc.).

於本發明之複合中間體中，基質樹脂與纖維束之重量比(基質樹脂/纖維束)就成形體強度等觀點而言，較佳為10/90~90/10，進而較佳為20/80~70/30，尤佳為30/70~60/40。於複合中間體含有觸媒之情形時，觸媒之含有率就成形體強度等觀點而言，相對於基質樹脂較佳為0.01~10重量%，進而較佳為0.1~5重量%，尤佳為1~3重量%。 In the composite intermediate of the present invention, the weight ratio of the matrix resin to the fiber bundle (matrix resin/fiber bundle) is preferably from 10/90 to 90/10, more preferably from 20%, from the viewpoint of the strength of the molded body and the like. 80~70/30, especially good for 30/70~60/40. In the case where the composite intermediate contains a catalyst, the content of the catalyst is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the strength of the molded body. It is 1 to 3% by weight.

複合中間體可藉由使熱熔融(熔融溫度：60~150℃)之基質樹脂、或利用溶劑(丙酮、甲基乙基酮、甲基異丁基酮、甲苯、二甲苯及乙酸乙酯等)進行稀釋之基質樹脂含浸於纖維束中而製造。於使用溶劑 之情形時，較佳為使預浸體乾燥而去除溶劑。 The composite intermediate can be thermally melted (melting temperature: 60 to 150 ° C) of a matrix resin or a solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethyl acetate, etc.) The matrix resin to be diluted is impregnated into the fiber bundle to be produced. Using solvent In the case of the case, it is preferred to dry the prepreg to remove the solvent.

本發明之纖維強化複合材料係將上述複合中間體成形而獲得。於基質樹脂為熱塑性樹脂之情形時，可藉由將預浸體加熱成形，並於常溫下固化而製成成形體。於基質樹脂為熱硬化性樹脂之情形時，可藉由將預浸體加熱成形，並使之硬化而製成成形體。硬化雖然無需完全進行，但較佳為硬化至成形體可維持形狀之程度。成形後，亦可進一步加熱而使之完全硬化。加熱成形之方法並無特別限定，例如可列舉：長絲纏繞成形法(一面對旋轉之心軸施加張力一面捲繞並進行加熱成形之方法)、加壓成形法(將預浸體片積層並進行加熱成形之方法)、高壓釜法(對模具施加壓力，壓抵預浸體片並進行加熱成形之方法)及將短切纖維或磨碎纖維與基質樹脂混合並進行射出成形之方法等。 The fiber-reinforced composite material of the present invention is obtained by molding the above composite intermediate. When the matrix resin is a thermoplastic resin, the preform can be formed by heat-forming the prepreg and curing at normal temperature. In the case where the matrix resin is a thermosetting resin, the preform can be formed by heat-forming and pre-hardening the prepreg. Although hardening does not need to be completely performed, it is preferably hardened until the molded body can maintain its shape. After forming, it can be further heated to completely harden it. The method of the thermoforming is not particularly limited, and examples thereof include a filament winding forming method (a method of winding and applying heat forming while applying a tension to a rotating mandrel), and a press forming method (prepreg sheeting) And a method of performing heat forming), an autoclave method (a method of applying pressure to a mold, pressing against a prepreg sheet and performing heat forming), and a method of mixing chopped fibers or ground fibers with a matrix resin and performing injection molding. .

[實施例] [Examples]

以下，藉由製造例及實施例進而說明本發明，但本發明並不限定於該等。 Hereinafter, the present invention will be further described by way of Production Examples and Examples, but the present invention is not limited thereto.

[<製造例1雙酚A之EO 30莫耳加成物之製造> [Production Example 1 Production of EO 30 Moer Additive of Bisphenol A>

於具備攪拌機、加熱冷卻裝置及滴液筒之耐壓反應容器中，投入雙酚A228重量份(1莫耳份)、甲苯400重量份及氫氧化鉀2重量份，而進行氮氣置換。升溫至100℃，一面以使壓力成為0.5MPaG以下之方式進行調整，一面歷時6小時滴加EO 1320重量份(30莫耳份)，然後於120℃熟化3小時，並於-0.1MPa下將甲苯去除。繼而冷卻至100℃後，投入吸附處理劑「Kyoword 600」[協和化學工業(股份有限公司)製造]30重量份，於100℃攪拌1小時而進行處理，其後將吸附處理劑過濾，而獲得雙酚A之EO 30 莫耳加成物。 In a pressure-resistant reaction vessel equipped with a stirrer, a heating and cooling device, and a drip tube, 228 parts by weight of bisphenol A (1 part by mole), 400 parts by weight of toluene, and 2 parts by weight of potassium hydroxide were charged, and nitrogen substitution was performed. The temperature was raised to 100 ° C, and the pressure was adjusted to 0.5 MPaG or less, and 1320 parts by weight of EO (30 mole parts) was added dropwise over 6 hours, and then aged at 120 ° C for 3 hours, and at -0.1 MPa. Toluene removal. After cooling to 100 ° C, 30 parts by weight of an adsorption treatment agent "Kyoword 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) was placed, and the mixture was stirred at 100 ° C for 1 hour to carry out treatment, and then the adsorption treatment agent was filtered to obtain EO 30 of Bisphenol A Moer add product.

<製造例2雙酚A之EO 3莫耳加成物之製造> <Production Example 2 Production of EO 3 Molar Additive of Bisphenol A>

將EO 1320重量份(30莫耳份)變更為132重量份(3莫耳份)，除此以外，以與製造例1相同之方式獲得雙酚A之EO 3莫耳加成物360重量份。 360 parts by weight of EO 3 molar addition of bisphenol A was obtained in the same manner as in Production Example 1 except that 1320 parts by weight (30 mole parts) of EO was changed to 132 parts by weight (3 mole parts). .

<製造例3聚酯樹脂(A-1)之製造> <Production Example 3 Production of Polyester Resin (A-1)>

將雙酚A之EO 2莫耳加成物「Newpol BPE-20」[三洋化成工業(股份有限公司)製造]316重量份(1莫耳份)、對苯二甲酸(a11)142重量份(0.86莫耳份)及草酸鈦酸鉀3重量份於玻璃反應容器中，一面於230℃減壓至0.001MPa並將水蒸餾去除，一面使之反應15小時。於反應混合物進而添加聚乙二醇(b11)「PEG-1000」[三洋化成工業(股份有限公司)製造]263重量份(0.26莫耳份)，並於150℃下於常壓下使之反應2小時，而獲得聚酯樹脂(A-1)690重量份。 316 parts by weight of EO 2 molar additive of bisphenol A (manufactured by Sanyo Chemical Industry Co., Ltd.), 142 parts by weight of terephthalic acid (a11), and 142 parts by weight of terephthalic acid (a11) 3 parts by weight of 0.86 mole parts and potassium oxalate titanate were placed in a glass reaction vessel, and the pressure was reduced to 0.001 MPa at 230 ° C, and water was distilled off, and the reaction was allowed to proceed for 15 hours. Further, 263 parts by weight (0.26 mole parts) of polyethylene glycol (b11) "PEG-1000" [manufactured by Sanyo Chemical Industry Co., Ltd.] was added to the reaction mixture, and the reaction was carried out at 150 ° C under normal pressure. 2 hours, 690 parts by weight of the polyester resin (A-1) was obtained.

<製造例4聚酯樹脂(A-2)之製造> <Production Example 4 Production of Polyester Resin (A-2)>

將對苯二甲酸(a11)142重量份(0.86莫耳份)變更為163重量份(0.98莫耳份)，將聚乙二醇(b11)「PEG-1000」[三洋化成工業(股份有限公司)製造]263重量份(0.26莫耳份)變更為聚乙二醇「PEG-10000」[三洋化成工業(股份有限公司)製造]359重量份(0.04莫耳份)，除此以外，以與製造例3相同之方式獲得聚酯樹脂(A-2)803重量份。 142 parts by weight (0.86 mole parts) of terephthalic acid (a11) was changed to 163 parts by weight (0.98 mole parts), and polyethylene glycol (b11) "PEG-1000" [Sanyo Chemical Industry Co., Ltd. (manufactured) 263 parts by weight (0.26 mole parts) was changed to polyethylene glycol "PEG-10000" [manufactured by Sanyo Chemical Industry Co., Ltd.] 359 parts by weight (0.04 mole parts), and In the same manner as in Production Example 3, 803 parts by weight of the polyester resin (A-2) was obtained.

<製造例5聚酯樹脂(A-3)之製造> <Manufacturing Example 5 Production of Polyester Resin (A-3)>

將雙酚A之EO 6莫耳加成物「Newpol BPE-60」[三洋化成工業(股份有限公司)製造]492重量份(1莫耳份)、反丁烯二酸(a12)108重量份(0.93莫耳份)及草酸鈦酸鉀3重量份於玻璃反應容器中，一面於230℃減壓至 0.001MPa並將水蒸餾去除，一面使之反應15小時。於反應混合物進而添加聚乙二醇(b12)「PEG-2000」[三洋化成工業(股份有限公司)製造]480重量份(0.24莫耳份)，並於150℃、常壓下使之反應2小時，而獲得聚酯樹脂(A-3)1046重量份。 EO 6 molar addition product of bisphenol A "Newpol BPE-60" [manufactured by Sanyo Chemical Industry Co., Ltd.] 492 parts by weight (1 mole part), and fumaric acid (a12) 108 parts by weight (0.93 mol parts) and potassium oxalate titanate 3 parts by weight in a glass reaction vessel, one side at 230 ° C decompression to 0.001 MPa and water was distilled off and allowed to react for 15 hours. Further, 480 parts by weight (0.24 mole parts) of polyethylene glycol (b12) "PEG-2000" [manufactured by Sanyo Chemical Industry Co., Ltd.] was added to the reaction mixture, and the reaction was carried out at 150 ° C under normal pressure. In an hour, 1046 parts by weight of the polyester resin (A-3) was obtained.

<製造例6聚酯樹脂(A-4)之製造> <Production Example 6 Production of Polyester Resin (A-4)>

將雙酚A之PO 3莫耳加成物「Newpol BP-3P」[三洋化成工業(股份有限公司)製造]402重量份(1莫耳份)、對苯二甲酸(a11)156重量份(0.94莫耳份)及草酸鈦酸鉀3重量份於玻璃反應容器中，一面於230℃減壓至0.001MPa並將水蒸餾去除，一面使之反應15小時。於反應混合物進而添加製造例1之雙酚A之EO 30莫耳加成物(b13)222重量份(0.14莫耳份)，並於150℃、常壓下使之反應2小時，而獲得聚酯樹脂(A-4)745重量份。 The PO 3 molar addition product of bisphenol A, "Newpol BP-3P" [manufactured by Sanyo Chemical Industry Co., Ltd.], 402 parts by weight (1 mol) and terephthalic acid (a11) 156 parts by weight ( 3 parts by weight of 0.94 mole parts and potassium oxalate titanate were placed in a glass reaction vessel, and the pressure was reduced to 0.001 MPa at 230 ° C, and water was distilled off, and the reaction was allowed to proceed for 15 hours. Further, 222 parts by weight (0.14 mole parts) of the EO 30 molar addition product (b13) of the bisphenol A of Production Example 1 was added to the reaction mixture, and the mixture was reacted at 150 ° C under normal pressure for 2 hours to obtain a polymerization. The ester resin (A-4) was 745 parts by weight.

<製造例7聚酯樹脂(A-5)之製造> <Production Example 7 Production of Polyester Resin (A-5)>

將雙酚A之EO 2莫耳加成物「Newpol BPE-20」[三洋化成工業(股份有限公司)製造]316重量份(1莫耳份)、對苯二甲酸(a11)163重量份(0.98莫耳份)及草酸鈦酸鉀3重量份於玻璃反應容器中，一面於230℃減壓至0.001MPa並將水蒸餾去除，一面使之反應15小時。於反應混合物進而添加聚丙二醇之EO加成物(b14)「Newpol PE-108」[三洋化成工業(股份有限公司)製造]359重量份(0.02莫耳份)，並於150℃、常壓下使之反應2小時，而獲得聚酯樹脂(A-5)800重量份。 316 parts by weight of EO 2 molar additive of bisphenol A (manufactured by Sanyo Chemical Industry Co., Ltd.), 316 parts by weight of terephthalic acid (a11), and 163 parts by weight of terephthalic acid (a11) 3 parts by weight of 0.98 mole parts and potassium oxalate titanate were placed in a glass reaction vessel, and the pressure was reduced to 0.001 MPa at 230 ° C, and water was distilled off, and the reaction was allowed to proceed for 15 hours. In the reaction mixture, EO adduct (b14) "Newpol PE-108" (manufactured by Sanyo Chemical Industry Co., Ltd.) was added to 359 parts by weight (0.02 mol), and at 150 ° C under normal pressure. This was allowed to react for 2 hours to obtain 800 parts by weight of the polyester resin (A-5).

<製造例8聚酯樹脂(A'-2)之製造> <Production Example 8 Production of Polyester Resin (A'-2)>

將製造例2之雙酚A之EO 3莫耳加成物360重量份(1莫耳份)、反丁烯二酸(a12)64重量份(0.56莫耳份)及草酸鈦酸鉀3重量份於玻璃反應 容器中，一面於230℃減壓至0.001MPa並將水蒸餾去除，一面使之反應15小時，而獲得聚酯樹脂(A'-2)404重量份。 360 parts by weight of EO 3 molar addition of bisphenol A of Production Example 2 (1 mole), 64 parts by weight of fumaric acid (a12) (0.56 moles), and 3 parts by weight of potassium oxalate titanate Glass reaction In a container, the pressure was reduced to 0.001 MPa at 230 ° C, and water was distilled off, and the mixture was allowed to react for 15 hours to obtain 404 parts by weight of a polyester resin (A'-2).

<製造例9聚酯樹脂(A'-4)之製造> <Production Example 9 Production of Polyester Resin (A'-4)>

將聚乙二醇(b15)「PEG-6000S」[三洋化成工業(股份有限公司)製造]8300重量份(1莫耳份)、對苯二甲酸(a11)166重量份(1莫耳份)及草酸鈦酸鉀3重量份於玻璃反應容器中，一面於230℃減壓至0.001MPa並將水蒸餾去除，一面使之反應15小時，而獲得聚酯樹脂(A'-4)8430重量份。 Polyethylene glycol (b15) "PEG-6000S" [manufactured by Sanyo Chemical Industry Co., Ltd.] 8300 parts by weight (1 mole) and terephthalic acid (a11) 166 parts by weight (1 mole) And 3 parts by weight of potassium oxalate titanate in a glass reaction vessel, and the pressure was reduced to 0.001 MPa at 230 ° C, and water was distilled off, and reacted for 15 hours to obtain 8430 parts by weight of a polyester resin (A'-4). .

<製造例10封端異氰酸酯(B-1)之製造> <Production Example 10 Production of blocked isocyanate (B-1)>

於具備攪拌機、加熱冷卻裝置及滴液筒之耐壓反應容器中，投入TDI 174重量份(1莫耳份)及甲苯400重量份，並於氮氣置換後密閉。於攪拌下一面以使溫度成為30℃以下之方式進行調整，一面滴加二甲基胺90重量份(2莫耳份)。滴加完畢後，於30℃至40℃之溫度範圍持續攪拌1小時，藉由過濾將甲苯去除，並於室溫下使之乾燥，藉此獲得封端異氰酸酯(B-1)。 In a pressure-resistant reaction vessel equipped with a stirrer, a heating and cooling device, and a drip tube, 174 parts by weight (1 mol) of TDI and 400 parts by weight of toluene were charged, and the mixture was sealed with nitrogen and sealed. While stirring, the temperature was adjusted to 30 ° C or less, and 90 parts by weight of dimethylamine (2 mole parts) was added dropwise. After completion of the dropwise addition, stirring was continued for 1 hour at a temperature ranging from 30 ° C to 40 ° C, toluene was removed by filtration, and dried at room temperature, whereby blocked isocyanate (B-1) was obtained.

<製造例11封端異氰酸酯(B-2)之製造> <Production Example 11 Production of blocked isocyanate (B-2)>

於具備攪拌機、滴液漏斗之燒瓶中，添加MDI 250重量份(1莫耳份)及四氫呋喃424重量份，於氮氣環境下，於30℃以下滴加甲基乙基酮肟174重量份(2莫耳份)，滴加完畢後，於40℃攪拌3小時，而獲得封端異氰酸酯(B-2)。 250 parts by weight of MDI (1 part molar) and 424 parts by weight of tetrahydrofuran were added to a flask equipped with a stirrer and a dropping funnel, and 174 parts by weight of methyl ethyl ketone oxime was added dropwise at 30 ° C or less under a nitrogen atmosphere (2) The molar fraction was stirred at 40 ° C for 3 hours to obtain a blocked isocyanate (B-2).

表1中揭示聚酯樹脂之HLB、30℃下之黏度、酯基濃度、二醇(b)之種類及每1種二醇之氧乙烯基之平均個數。表1中所記載之各成分及黏度之測定方法如下所述。 Table 1 shows the HLB of the polyester resin, the viscosity at 30 ° C, the ester group concentration, the type of the diol (b), and the average number of oxyethylene groups per diol. The measurement methods of the respective components and the viscosity described in Table 1 are as follows.

聚酯樹脂(A) Polyester resin (A)

(A'-1)：聚乙二醇二月桂酸酯「Ionet DL-200」[三洋化成工業(股份有限公司)製造] (A'-1): Polyethylene glycol dilaurate "Ionet DL-200" [Made in Sanyo Chemical Industry Co., Ltd.]

(A'-3)：聚乳酸「RESOMER R202S」(Aldrich公司製造) (A'-3): Polylactic acid "RESOMER R202S" (made by Aldrich)

<黏度之測定方法> <Method for measuring viscosity>

利用黏彈性測定裝置(Anton Paar Japan股份有限公司製造之「MCR 302」)，於以下之條件測定複數黏度，並讀取於30℃之黏度。 Using a viscoelasticity measuring apparatus ("MCR 302" manufactured by Anton Paar Japan Co., Ltd.), the complex viscosity was measured under the following conditions, and the viscosity at 30 ° C was read.

樣品固定夾具：直徑25mm圓盤 Sample fixing fixture: 25mm diameter disc

間隙間距離：0.25mm Distance between gaps: 0.25mm

應變：1% Strain: 1%

頻率：1Hz Frequency: 1Hz

測定溫度：20℃~100℃(升溫速度：5℃/min) Measurement temperature: 20 ° C ~ 100 ° C (temperature increase rate: 5 ° C / min)

製作具有表2及表3所記載之份數(有效成分換算)之纖維用集束劑組成物。將該纖維用集束劑組成物與水混合，而製作固形物成分濃度1.5重量%之纖維用集束劑組成物水分散液(實施例1~20、比較例1~8)，並對乳化穩定性、碳纖維束之集束性、起毛及複合材料之拉伸強度進行評價。再者，實施例及比較例中所使用之各成分如下所述。 A fiber sizing agent composition having the parts (in terms of active ingredient conversion) described in Tables 2 and 3 was produced. This fiber was mixed with water using a sizing agent composition to prepare an aqueous dispersion of a fiber sizing agent composition having a solid content concentration of 1.5% by weight (Examples 1 to 20 and Comparative Examples 1 to 8), and the emulsion stability was obtained. The bundleability of carbon fiber bundles, fuzzing and tensile strength of composite materials were evaluated. Further, the respective components used in the examples and comparative examples are as follows.

反應性化合物(B) Reactive compound (B)

(B-3)：經ε-己內醯胺封端之TDI「Desmodur BL 1100/1」Sumika Bayer Urethane(股份有限公司)製造] (B-3): TDI "Desmodur BL 1100/1" manufactured by ε-caprolactam, manufactured by Sumika Bayer Urethane (company)

(B-4)：經甲基乙基酮肟封端之HDI「Sumidur BL 3175」Sumika Bayer Urethane(股份有限公司)製造](濃度：75%) (B-4): HDI "Sumidur BL 3175" Sumika Bayer Urethane (company) manufactured by methyl ethyl ketoxime] (concentration: 75%)

(B-5)：經活性亞甲基封端之HDI「Desmodur BL 3475 BA/SN」Sumika Bayer Urethane(股份有限公司)製造](濃度：75%) (B-5): manufactured by active methylene-terminated HDI "Desmodur BL 3475 BA/SN" Sumika Bayer Urethane (company)] (concentration: 75%)

(B-6)：經胺封端之HDI「Desmodur BL 3575/1 MPA/SN」Sumika Bayer Urethane(股份有限公司)製造](濃度：75%) (B-6): manufactured by amine-terminated HDI "Desmodur BL 3575/1 MPA/SN" Sumika Bayer Urethane (company)] (concentration: 75%)

(B-7)：3-(3,4-二氯苯基)-1,1-二甲基脲「DCMU」[保土谷化學(股份有限公司)製造] (B-7): 3-(3,4-Dichlorophenyl)-1,1-dimethylurea "DCMU" [Manufactured by Hodogaya Chemical Co., Ltd.]

(B-8)：三乙醇胺[東京化成工業(股份有限公司)製造] (B-8): Triethanolamine [Manufactured by Tokyo Chemical Industry Co., Ltd.]

(B-9)：DBU-辛酸鹽「U-CAT SA102」[San-Apro(股份有限公司)製造] (B-9): DBU-octanoate "U-CAT SA102" [manufactured by San-Apro Co., Ltd.]

(B-10)：溴化苄基三甲基銨[東京化成工業(股份有限公司)製造] (B-10): benzyltrimethylammonium bromide [manufactured by Tokyo Chemical Industry Co., Ltd.]

(B-11)：溴化四丁基鏻[東京化成工業(股份有限公司)製造] (B-11): tetrabutylphosphonium bromide [manufactured by Tokyo Chemical Industry Co., Ltd.]

(B-12)：三苯基膦[東京化成工業(股份有限公司)製造] (B-12): Triphenylphosphine [Manufactured by Tokyo Chemical Industry Co., Ltd.]

樹脂(C) Resin (C)

(C-1)：雙酚A之二縮水甘油醚「JER834」[三菱化學(股份有限公司)製造] (C-1): bisphenol A diglycidyl ether "JER834" [Mitsubishi Chemical Co., Ltd.]

(C-2)：苯酚酚醛清漆之二縮水甘油醚「JER152」[三菱化學(股份有限公司)製造] (C-2): diglycidyl ether of phenol novolac varnish "JER152" [Made in Mitsubishi Chemical Co., Ltd.]

(C-3)：N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷「Araldite MY721」[Huntsman Advanced Materials公司製造] (C-3): N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane "Araldite MY721" [manufactured by Huntsman Advanced Materials Co., Ltd.]

(C-4)：聚氧伸烷基之二縮水甘油醚「DENACOL EX-946L」[Nagase Chemtex(股份有限公司)製造] (C-4): polyoxyalkylene diglycidyl ether "DENACOL EX-946L" [manufactured by Nagase Chemtex Co., Ltd.]

(C-5)：胺酯改質環氧樹脂「Adeka Resin EPU-6」[ADEKA股份有限公司製造] (C-5): Amine modified epoxy resin "Adeka Resin EPU-6" [Manufactured by ADEKA Co., Ltd.]

(C-6)：烷基單縮水甘油醚「Epolight M-1230」[共榮社化學(股份有限公司)製造] (C-6): Alkyl monoglycidyl ether "Epolight M-1230" [manufactured by Kyoeisha Chemical Co., Ltd.]

(C-7)：丁二烯-腈橡膠改質環氧樹脂「Epiclon TSR-601」[大日本油墨化學工業(股份有限公司)製造] (C-7): Butadiene-Nitrile Rubber Modified Epoxy Resin "Epiclon TSR-601" [Manufactured by Dainippon Ink Chemical Industry Co., Ltd.]

界面活性劑(D) Surfactant (D)

(D-1)：苯乙烯化苯酚之環氧丙烷環氧乙烷加成物「Soprophor 796/P」[Solvay Nicca(股份有限公司)製造] (D-1): propylene oxide ethylene oxide adduct of styrenated phenol "Soprophor 796/P" [Manufactured by Solvay Nicca Co., Ltd.]

<乳化穩定性之評價> <Evaluation of emulsion stability>

藉由在攪拌下對纖維用集束劑組成物10g添加40℃之水190g，而製作集束劑稀釋液。將該集束劑稀釋液調溫至40℃，利用均質攪拌機(特殊機 化工業公司製造之TK Robomix)施加8,000rpm、10分鐘之剪切。利用400目之金屬篩網(約10cm×10cm；重量約5g)對其進行過濾，並測定金屬篩網之過濾前後之增加部分重量(g)。增加部分重量越少意味著乳化穩定性越優異。 A concentrator diluent was prepared by adding 190 g of water at 40 ° C to 10 g of the fiber sizing agent composition under stirring. Adjust the sizing agent dilution to 40 ° C, using a homomixer (special machine TK Robomix manufactured by Chemical Industry Co., Ltd. applied a shear of 8,000 rpm for 10 minutes. It was filtered using a 400 mesh metal mesh (about 10 cm x 10 cm; weight about 5 g), and the weight gain (g) of the metal mesh before and after filtration was measured. Increasing the partial weight means that the emulsion stability is more excellent.

<集束性之評價> <Evaluation of clustering>

將未處理碳纖維(纖度800tex，長絲數12,000根)浸漬於固形物成分濃度1.5重量%之纖維用集束劑組成物水分散液(實施例1~20、比較例1~8)，而使之含浸集束劑，於120℃進行熱風乾燥3分鐘而製作碳纖維束。 The untreated carbon fiber (denier 800 tex, number of filaments 12,000) was immersed in an aqueous dispersion of a fiber sizing agent composition having a solid content concentration of 1.5% by weight (Examples 1 to 20 and Comparative Examples 1 to 8). The impregnating sizing agent was dried by hot air at 120 ° C for 3 minutes to prepare a carbon fiber bundle.

依據JIS L1096-1999 8.19.1 A法(45°懸臂法)對所獲得之碳纖維束之集束性進行評價。數值越大意味著集束性越優異。 The bundleability of the obtained carbon fiber bundle was evaluated in accordance with JIS L1096-1999 8.19.1 A method (45° cantilever method). A larger value means that the bundling property is superior.

<起毛之測定> <Measurement of raising hair>

將直徑2mm之經鍍鉻之不鏽鋼棒以15mm間隔，且以碳纖維束以120°之接觸角與其表面接觸並且通過其表面之方式錯開地配置5根。於該不鏽鋼棒間錯開地架設碳纖維束，並施加1kg重之張力。於捲取輥正前方利用2片施加有1kg重之荷重之10cm×10cm之胺酯泡沫體夾住碳纖維束，並以1m/min之速度進行5分鐘摩擦。測定其間附著於胺酯泡沫體之絨毛之重量。數值越小，意味著纖維束之起毛越得到抑制，絨毛特性越優異。 A chrome-plated stainless steel rod having a diameter of 2 mm was placed at intervals of 15 mm, and five carbon fiber bundles were brought into contact with the surface at a contact angle of 120° and five of them were staggered by the surface thereof. A carbon fiber bundle was placed between the stainless steel rods in a staggered manner, and a tension of 1 kg was applied. The carbon fiber bundle was sandwiched between two sheets of a 10 cm × 10 cm amine ester foam to which a load of 1 kg was applied in front of the take-up roll, and rubbed at a speed of 1 m/min for 5 minutes. The weight of the fluff attached to the amine ester foam was measured. The smaller the value, the more the fluffing of the fiber bundle is suppressed, and the more excellent the fluff characteristics.

<拉伸強度之測定> <Measurement of tensile strength>

將基質樹脂(混合有雙酚A型環氧樹脂「JER828」[Japan Epoxy Resin股份有限公司製造]100重量份、BF3單乙基胺鹽3重量份者)較薄地均勻地塗佈於脫模紙上而製作熱熔片。將上漿處理後之碳纖維束並列地拉齊，配置於該基質樹脂上，並含浸基質樹脂，藉此製作基質樹脂含有率約35質量 %、纖維單位面積重量195g/m2之預浸體。 The matrix resin (100 parts by weight of bisphenol A type epoxy resin "manufactured by Japan Epoxy Resin Co., Ltd." and 3 parts by weight of BF 3 monoethylamine salt) was uniformly applied to the release mold. Make a hot melt sheet on paper. The carbon fiber bundles after the sizing treatment were placed side by side, placed on the matrix resin, and impregnated with the matrix resin to prepare a prepreg having a matrix resin content of about 35% by mass and a fiber basis weight of 195 g/m 2 .

對於所獲得之預浸體，將碳纖維束之朝向沿一方向對齊並進行積層，使用高壓釜進行加熱、加壓硬化(於壓力0.59MPa下，以15℃/min之升溫速度自室溫升溫至180℃，並保持2小時)，而製作厚度1mm之硬化板(碳纖維強化複合材料)。繼而，自所獲得之硬化板切下長度230mm、寬度12.5mm之試片，依據JIS K7073對該試片測定0°拉伸強度。 For the prepreg obtained, the carbon fiber bundles were aligned in one direction and laminated, and heated and press hardened using an autoclave (heating from room temperature to 180 at a pressure of 0.59 MPa at a heating rate of 15 ° C/min) °C, and kept for 2 hours), and a hardened sheet (carbon fiber reinforced composite material) having a thickness of 1 mm was produced. Then, a test piece having a length of 230 mm and a width of 12.5 mm was cut out from the obtained hardened sheet, and the tensile strength of the test piece was measured in accordance with JIS K7073.

拉伸試驗機之拉伸速度設為13mm/min，測定次數設為n=5，由各測定值算出平均值，設為各例之拉伸強度。 The tensile speed of the tensile tester was set to 13 mm/min, and the number of measurements was set to n=5, and the average value was calculated from each measured value, and the tensile strength of each example was set.

由表2及表3可知，利用本發明之纖維用集束劑組成物(實 施例1~20)進行處理而獲得之纖維束顯示出優異之乳化穩定性、集束性及絨毛特性。進而，由上述纖維束與基質樹脂獲得之複合材料之拉伸強度優異。如比較例1及2所示，不含聚酯樹脂(A)或反應性化合物(B)之任一者之纖維用集束劑組成物雖然集束性充分，但拉伸強度較低。如比較例2所示，於不含聚酯樹脂之情形時，乳化穩定性及絨毛特性不足。如比較例3~6所示，於聚酯樹脂之黏度過低之情形時或過高之情形時，雖然亦存在賦予優異之乳化穩定性之集束劑，但抑制起毛及拉伸強度不充分。如比較例7及8所示，於不含聚酯樹脂(A)及反應性化合物(B)之任一者之情形時，雖然亦存在賦予優異之拉伸強度之集束劑，但無法同時實現集束性與拉伸強度。又，比較例7及8之乳化穩定性及起毛惡化。 It can be seen from Table 2 and Table 3 that the sizing agent composition for fibers of the present invention is used. The fiber bundles obtained by the treatment of Examples 1 to 20) exhibited excellent emulsion stability, bundling property, and fluff characteristics. Further, the composite material obtained from the above fiber bundle and the matrix resin is excellent in tensile strength. As shown in Comparative Examples 1 and 2, the fiber sizing agent composition which does not contain any of the polyester resin (A) or the reactive compound (B) has sufficient bundle strength, but has low tensile strength. As shown in Comparative Example 2, in the case where the polyester resin was not contained, the emulsion stability and the fluff characteristics were insufficient. As shown in Comparative Examples 3 to 6, when the viscosity of the polyester resin is too low or too high, the sizing agent which imparts excellent emulsion stability is also provided, but the fluffing and the tensile strength are insufficient. As shown in Comparative Examples 7 and 8, in the case where neither the polyester resin (A) nor the reactive compound (B) is contained, although a sizing agent which imparts excellent tensile strength is also present, it cannot be simultaneously achieved. Bundling and tensile strength. Further, the emulsion stability and the fuzzing of Comparative Examples 7 and 8 were deteriorated.

[產業上之可利用性] [Industrial availability]

將由使用本發明之纖維用集束劑組成物製造之纖維束、與基質樹脂所獲得之複合中間體成形而成之纖維強化複合材料可適宜地用作各種土木、建築用材料、運輸機用材料、運動用品材料及發電裝置用材料等。 The fiber-reinforced composite material obtained by molding the fiber bundle produced by using the fiber sizing agent composition of the present invention and the composite intermediate obtained from the matrix resin can be suitably used as various materials for civil engineering, construction materials, transportation materials, and sports. Supplies materials and materials for power generation equipment.

Claims (14)

一種纖維用集束劑組成物，其含有聚酯樹脂(A)及反應性化合物(B)，並且聚酯樹脂(A)係HLB為4~18、於30℃之黏度為10~1,000,000Pa‧s之聚酯樹脂，反應性化合物(B)為選自由封端異氰酸酯、三級胺、三級胺鹽、四級銨鹽、四級鏻鹽及膦化合物所組成之群中之至少1種反應性化合物，纖維用集束劑組成物中之聚酯樹脂(A)與反應性化合物(B)之重量比[(A)/(B)]為99.9/0.1~10/90。 A fiber sizing agent composition comprising a polyester resin (A) and a reactive compound (B), and the polyester resin (A) has an HLB of 4 to 18 and a viscosity at 30 ° C of 10 to 1,000,000 Pa ‧ s The polyester resin, the reactive compound (B) is at least one selected from the group consisting of a blocked isocyanate, a tertiary amine, a tertiary amine salt, a quaternary ammonium salt, a quaternary phosphonium salt, and a phosphine compound. The weight ratio [(A)/(B)] of the polyester resin (A) to the reactive compound (B) in the compound and fiber sizing agent composition is 99.9/0.1 to 10/90. 如申請專利範圍第1項之纖維用集束劑組成物，其中，上述聚酯樹脂(A)中之酯基濃度基於上述聚酯樹脂(A)之重量，為10mmol/g以下。 The fiber sizing agent composition according to the first aspect of the invention, wherein the ester group concentration in the polyester resin (A) is 10 mmol/g or less based on the weight of the polyester resin (A). 如申請專利範圍第1或2項之纖維用集束劑組成物，其中，上述聚酯樹脂(A)為二羧酸(a1)及/或二羧酸之酸酐(a2)、與二醇(b)之縮聚合物。 The fiber sizing agent composition according to claim 1 or 2, wherein the polyester resin (A) is an acid anhydride (a2) of a dicarboxylic acid (a1) and/or a dicarboxylic acid, and a diol (b) ) a shrinking polymer. 如申請專利範圍第3項之纖維用集束劑組成物，其中，上述二醇(b)中之至少1種為具有平均5~200個氧乙烯基之二醇(b1)。 The fiber sizing agent composition according to the third aspect of the invention, wherein at least one of the diols (b) is a diol (b1) having an average of 5 to 200 oxyethylene groups. 如申請專利範圍第4項之纖維用集束劑組成物，其中，上述二醇(b1)為雙酚A之環氧乙烷加成物及/或乙二醇之環氧乙烷加成物。 The fiber sizing agent composition according to claim 4, wherein the diol (b1) is an ethylene oxide adduct of bisphenol A and/or an ethylene oxide adduct of ethylene glycol. 如申請專利範圍第1至5項中任一項之纖維用集束劑組成物，其中，上述反應性化合物(B)為封端異氰酸酯。 The fiber sizing agent composition according to any one of claims 1 to 5, wherein the reactive compound (B) is a blocked isocyanate. 如申請專利範圍第6項之纖維用集束劑組成物，其中，上述封端異氰酸酯之封端化劑為選自由醇、酚、活性亞甲基、肟、內醯胺及胺所組成之群中之至少1種封端化劑。 The fiber sizing agent composition according to claim 6, wherein the blocked isocyanate blocking agent is selected from the group consisting of alcohols, phenols, active methylene groups, hydrazines, lactams and amines. At least one blocking agent. 如申請專利範圍第1至7項中任一項之纖維用集束劑組成物，其進而含有上述聚酯樹脂(A)以外之樹脂(C)，樹脂(C)為選自由上述聚酯樹脂(A)以外之聚酯樹脂、環氧樹脂、聚胺酯樹脂(polyurethane resin)、(甲基)丙烯酸酯樹脂、不飽和聚酯樹脂及聚醯胺樹脂所組成之群中之至少1種。 The fiber sizing agent composition according to any one of claims 1 to 7, which further comprises a resin (C) other than the above polyester resin (A), the resin (C) being selected from the above polyester resin ( At least one of a group consisting of a polyester resin, an epoxy resin, a polyurethane resin, a (meth) acrylate resin, an unsaturated polyester resin, and a polyamide resin other than A). 如申請專利範圍第1至8項中任一項之纖維用集束劑組成物，其進而含有界面活性劑(D)，界面活性劑(D)為選自由非離子界面活性劑、陰離子界面活性劑、陽離子界面活性劑及兩性界面活性劑所組成之群中之至少1種。 The fiber sizing agent composition according to any one of claims 1 to 8, which further comprises a surfactant (D), the surfactant (D) being selected from the group consisting of a nonionic surfactant and an anionic surfactant. At least one of the group consisting of a cationic surfactant and an amphoteric surfactant. 一種纖維用集束劑分散體，係使申請專利範圍第1至9項中任一項之纖維用集束劑組成物分散於水或有機溶劑而成。 A fiber sizing agent dispersion obtained by dispersing a fiber sizing agent composition according to any one of claims 1 to 9 in water or an organic solvent. 一種纖維用集束劑溶液，係使申請專利範圍第1至9項中任一項之纖維用集束劑組成物溶解於水或有機溶劑而成。 A fiber sizing agent solution obtained by dissolving a fiber sizing agent composition according to any one of claims 1 to 9 in water or an organic solvent. 一種纖維束之製造方法，係利用申請專利範圍第10項之纖維用集束劑分散體或申請專利範圍第11項之纖維用集束劑溶液，對選自由碳纖維、玻璃纖維、聚芳醯胺纖維、陶瓷纖維、金屬纖維、礦物纖維及礦渣纖維(slag fiber)所組成之群中之至少1種纖維進行處理而獲得纖維束。 A method for producing a fiber bundle, which is characterized in that the fiber sizing agent dispersion of claim 10 or the fiber sizing agent solution of claim 11 is selected from the group consisting of carbon fiber, glass fiber, polyarsenamide fiber, At least one of the group consisting of ceramic fiber, metal fiber, mineral fiber, and slag fiber is treated to obtain a fiber bundle. 一種複合中間體，係由經申請專利範圍第12項之製造方法獲得之纖維 束與基質樹脂而獲得。 A composite intermediate obtained from the production method of the method of claim 12 The bundle is obtained with a matrix resin. 一種纖維強化複合材料，係將申請專利範圍第13項之複合中間體成形而成。 A fiber reinforced composite material obtained by forming a composite intermediate of claim 13 of the patent application.
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